Polymer 231 (2021) 124111

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Zwitterionic dual-network strategy for highly stretchable and transparent

ionic conductor
Ji Lan a, Bo Zhou a, Chenxiao Yin a, Lin Weng a, Wei Ni b, **, Ling-Ying Shi a, *
a
College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, China
b
State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, ANSTEEL Research Institute of Vanadium & Titanium (Iron & Steel), Chengdu,
610031, China

A R T I C L E I N F O A B S T R A C T

Keywords: The development of flexible electronic devices depends on the research of stretchable conductive materials. In
Dual-network this work, we report a green and transparent ionic conductor with high stretchability based on green deep
Deep eutectic solvents eutectic solvents (DESs) and biocompatible zwitterionic polymer. The dual-network (DN) strategy was achieved
Zwitterionic polymer
by two-step UV-initiated polymerization, and the DN ion gels consisting of the physically cross-linked zwitter­
Flexible strain sensor
ionic poly(3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate) (PDMAPS) and chemically cross-
linked poly(2-hydroxyethyl methacrylate) (PHEMA) were prepared, using choline chloride/ethylene glycol
(ChCl/EG) DESs as solvents. The prepared DN ion gels present outstanding tensile properties (breaking strain
over 1000%), high transparency (>90%), good room temperature ionic conductivity (0.315 S m− 1), and good
fatigue resistance. In addition, due to the ultra-low volatility and low freezing point of the ChCl/EG DESs, the DN
ion gel shows high stability and frost resistance (− 60 ◦ C). Finally, the performance of the DN ionic gel-based
flexible strain sensor is investigated to evaluate its application potential in wearable flexible electronic de­
vices. The DN ion gel strain sensor can sensitively and stably monitor human motions. The outstanding char­
acteristics such as non-toxicity and biocompatibility of both the conductive filler and polymer matrix for
preparing the DN ion gels in this work provide a new view for the development of green flexible conductive
devices with high performance and multiple functions.

1. Introduction
Transparent and stretchable conductive gels are important core
materials for flexible electronics that requires both optical transparences
and high conductivity even at severe strain deformation [1–5]. A
tremendous research trends on the stretchable conductors are ionic
polymer gels such as ionic hydrogels and ionogels [6–10]. The
conductive ionic hydrogels can be facilely prepared by using salt solu­
tion as gelation precursor or by salt-soaking strategy, and they show
excellent biocompatibility, high stretchability and adjustable mechani­
cal properties, attractive for manufacturing equipment in flexible elec­
tronics [11–14]. However, the hydrogel is susceptible to dehydration in
the ambient environment and to loss the flexibility due to the freezing of
water at the subzero environment, which influence the long-term
durability and operating temperature range [15,16]. Fixing the ionic
liquids (ILs) instead of water in gelling matrix produces ionogels with
high stability, and a wide range of ILs consisting of an organic cation
such as alkylimidazolium, alkylpyridinium, alkylphosphonium or alky­
lammonium, and an organic or inorganic anion such as tetra­
fluoroborate, hexafluorophosphate, or bis(trifluoromethylsulfonyl)
imide can be selectively used. The ILs based ion gels possess the prop­
erties of chemical stability, high ionic conductivity, low vapor pressure
and extreme temperature resistance [8,17,18]. However, the high
manufacturing cost and complicated preparation process of ILs greatly
increase the cost of the ionogels, and the potential biological toxicity of
the conventional ILs may cause harm to the human body when used as
implanted and wearable devices [19,20]. Therefore, nontoxic, more
economical and stable conductive ionic gels are demanded for the
development of green flexible electronic devices.
Deep eutectic solvents (DESs) are a new class of green ionic liquids
[21], which are binary or ternary systems consisting of hydrogen bond
donors (HBD) and hydrogen bond acceptors (HBA). Compared with

* Corresponding author.
** Corresponding author.
E-mail addresses: niwei@iccas.ac.cn (W. Ni), shilingying@scu.edu.cn (L.-Y. Shi).

https://doi.org/10.1016/j.polymer.2021.124111
Received 22 June 2021; Received in revised form 16 August 2021; Accepted 18 August 2021
Available online 21 August 2021
0032-3861/© 2021 Elsevier Ltd. All rights reserved.
J. Lan et al.
conventional ILs, DESs not only have the advantages of stability, high
ionic conductivity, relatively wide liquid range, non-volatile and
nonflammability, but also has the merits of low cost, easy preparation
and good biocompatibility [20,22]. The DESs have been utilized as
green and stable conductive fillers to fabricate strain sensors and elec­
trolytes [23,24]. For example, Hong et al. prepared an ion gel for strain
sensor and supercapacitor electrolyte through the radical polymeriza­
tion of acrylamide monomer with cellulose pulp as reinforcing agent in
the deep eutectic solvent system of choline chloride-urea-glycerol
(ChCl-U-G) [25]. Lai et al. reported a 3D printable ion gel strain sen­
sors prepared by photo-curing the mixture of cellulose nanocrystals
(CNCs), ChCl/EG (ethylene glycol) DESs, acrylic acid and Al3+ ions [26].
In addition to the consideration of conductivity, long-term resistance
and safety of the conductive fillers, the corresponding properties and
mechanical performance of the polymer matrix are also important
criteria for the application of ion gel materials as wearable stretchable
electronics.
Zwitterionic (ZI) polymers have emerged as a particular class of ion
gels matrix that can balance the mechanical properties and conductivity
[27]. The zwitterionic polymers contain both cationic and anionic
groups on the same monomer side chain [28], and the inter- and
intramolecular electrostatic interactions of ZI polymers provide physical
cross-linking and reduce the rigidity of materials. When ZI polymers are
used as the scaffold of ionic conductive materials, the zwitterionic
groups of the polymer networks have been demonstrated to promote
dissociation of ion sources and improve electrochemical performance
due to the favorable zwitterion− ion and zwitterion− zwitterion in­
teractions [29–31]. The unique properties of antifouling and good
biocompatibility of ZI polymers make them an ideal flexible material
substrate for wearable electronics [32–34]. However, most studies of ZI
polymers applied in flexible materials have been focused on hydrogels
and ionogels, but not yet in DESs ion gels. Moreover, the physically
cross-linked zwitterionic single network gels, e.g., poly(3-dimethyl
(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS), poly
(2-methacryloyloxyethyl phosphorylcholine) (PMPC) hydrogels [35],
were quite weak and their mechanical performances are not good
enough to meet the durability for long-term application [30,36].
Here, we synthesized a zwitterionic double-network (DN) ion gel and
a copolymer single network (SN) ion gel for comparison, integrating the
advantages of biocompatibility, high conductivity and good mechanical
performance in a wide temperature operating range. Poly(3-dimethyl
(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS) is a
representative betaine type zwitterionic polymer with good antibacte­
rial properties and biocompatibility, and is also an environmentally
friendly polymer matrix [33,35]. The DN ion gel consists of biocom­
patible PDMAPS and poly(2-hydroxyethyl methacrylate) (PHEMA) as
the substrates, and ChCl/EG DESs as conductive medium. The physically
cross-linked PDMAPS provides viscosity and high elasticity, the chemi­
cally cross-linked PHEMA improves the mechanical strength, and the
ChCl/EG DESs ensure the conductivity. The mechanical properties of the
DN network ion gel and the SN copolymer gels were tested and
compared. The DN ionic gel presents highly improved strength and
elasticity, high transparency (>90%), frost resistance (− 60 ◦ C) and good
stability. Finally, the DN ion gels were assembled into flexible strain
sensors and their performances to detect the movements of different
human limbs were characterized.
2. Experimental section
2.1. Materials
3-Dimethyl(methacryloyloxyethyl) ammonium propane sulfonate
(DMAPS, 95%) was purchased from Sigma-Aldrich. 2-Hydroxyethyl
methacrylate (HEMA, 96%), choline chloride (ChCl, 98%), poly
(ethylene glycol) dimethacrylate (PEGDMA) (Mn = 550 g mol− 1), 2-hy­
droxy-2-methylpropiophenone (photoinitiator 1173, 97%) and ethylene
2
Polymer 231 (2021) 124111
glycol (EG, >99%) were purchased from Aladdin Industrial Corporation.
The inhibitors in the HEMA and PEGDMA monomers were removed by
neutral alumina column chromatography.
2.2. Preparation of DESs
The DES was synthesized by using EG as hydrogen bond donor and
ChCl as hydrogen bond acceptor. More specifically, EG and ChCl were
mixed at a molar ratio of 2:1 and then the mixture was stirred and heated
to 100 ◦ C for 1 h. After cooling, the prepared DES remained a liquid and
was then stored in a vacuum desiccator.
2.3. Preparation of zwitterionic ion gel and DN hydrogel
Zwitterionic DN ion gel was prepared by two-step photo­
polymerization. Firstly, a certain amount of monomer DMAPS and
photoinitiator 1173 (0.2 mol% to monomer DMAPS) were dissolved in
the prepared DESs and stirred to obtain a homogeneous solution, which
was named as precursor solution A. The precursor solution A was irra­
diated for 1 h under 365 nm UV light to obtain viscous PDMAPS solution
in DESs. Then, an appropriate amount of monomer HEMA, cross-linking
agent PEGDMA (0.1 mol% to monomer HEMA) and photoinitiator 1173
(0.2 mol% to monomer HEMA) were dissolved in the prepared
PDMAPS/DESs solution, and the precursor solution B was obtained after
stirring evenly. Finally, the precursor solution B was injected into a
sealed mold composed of two glass plates and silicone rubber gaskets by
syringe, and exposed to 365 nm UV light for 1 h to obtain DN ion gel. The
formulation of DN ion gels is shown in Table S1 (Electronic Supple­
mentary Information, ESI†). Different DN ion gels were prepared by
changing the molar ratio of monomer DMAPS and HEMA, named DN1,
DN2, DN3, and DN4 ion gel, respectively.
DN hydrogel was prepared by the same method as that of DN ion gel,
used as control group. The only difference is that the DES is replaced by
1 mol/L ChCl aqueous solution with the same mass.
As shown in Table S2 (ESI†) for the preparation of SN ion gels,
DMAPS and HEMA was kept the same ratio as in DN ion gel via the one-
pot photoinitiated copolymerization, which is named SN1, SN2, SN3,
and SN4 ion gel. Specifically, DESs, cross-linking agent PEGDMA, pho­
toinitiator 1173, monomer DMAPS and HEMA were mixed evenly ac­
cording to a certain proportion, the mixed solution was transferred to a
mold, and the SN ion gel was obtained by irradiation for 1 h under 365
nm UV light.
2.4. Characterization
The morphology of the prepared ion gels was characterized using
scanning electron microscope (SEM) (FEI, USA) equipped with an en­
ergy dispersive X-ray (EDX) analyzer at an acceleration voltage of 20 kV.
The transmittance of 0.5 mm thick gels films in the visible light range
was characterized by the UV–Vis spectrophotometer (UV-3600, Shi­
madzu, Japan). The thermal behavior was investigated by thermogra­
vimetric analyser (TGA) (TG209F1, Netzsch, DE) with a heating rate of
10 ◦ C min− 1 under nitrogen. Differential scanning calorimetry (DSC)
data were obtained using a TA Instrument (DSC Q2000) with a scan rate
of 5 ◦ C min− 1 under dry nitrogen environment.
Mechanical performance test. Mechanical properties of the sam­
ples were characterized using INSTRON universal material experimental
machine (Model 5576, Instron Instruments, USA). The gels samples were
cut into dumbbell shapes (50 mm in length × 10 mm in width × 0.5 mm
in thickness, 20 mm gauge length and 4 mm inner width), and the tensile
speed of test was 100 mm min− 1. The temperature was strictly
controlled by the heating system of INSTRON machine and the liquid
nitrogen cooling system. Before the test, the sample is fixed and kept at
set temperature for more than 0.5 h to ensure accuracy.
Electrical performance test. The electrochemical performances of
ion gels were measured by CHI 760E electrochemical workstation. The
J. Lan et al. Polymer 231 (2021) 124111

temperatures of the samples were controlled by the universal testing Table 1

machine liquid nitrogen cooling system (to control the low tempera­ The monomer ratio and the DESs/polymer ratio for the SN and DN ion gels.
tures) and the hot stage heating system (to control the high tempera­ Sample DMAPS HEMA Young’s Fracture Fracture
tures). The conductivity (σ ) was measured by employing (mol%) (mol%) modulus E strength σb elongation εb
electrochemical impedance spectroscopy (EIS) with the frequency range (kPa) (kPa) (%)
of 1–105 Hz. The conductivity (σ) of ion gel was calculated by the SN1 10 90 10.5 29.3 455
equation σ = L/(R⋅S), where R, L and S are the resistance, length and DN1 10 90 80.6 204.5 527
cross-sectional area of the sample, respectively. The electrochemical SN2 20 80 5.7 16.7 428
DN2 20 80 48.8 179.5 686
window of DN ion gel was evaluated by linear sweep voltammetry (LSV) SN3 30 70 3.5 10.4 402
within the potential range of 0–5 V at a scanning speed of 10 mV s− 1. The DN3 30 70 24.6 132.3 802
current signals of strain sensors were measured in realtime with a SN4 40 60 1.6 6.0 420
Keithley 2601B system source meter. The size of ion gel for preparation DN4 40 60 17.4 123.0 1033
of the strain sensor was in the dimension of length × width × height
~2.5 × 1 × 0.1 cm3.
the chemical cross-linking agents PEGDMA accounts 0.1% mole ratio in
monomer for both PDMAPS-co-HEMA and PHEMA.
3. Results and discussion
The mechanical properties are very important for the practical
application of iongels as flexible devices. To illustrate the design prin­
3.1. Synthesis of zwitterionic copolymer SN and DN DESs ion gels, and
ciples of the DN network, we investigated the mechanical performances
the mechanical performances comparison
of the PDMAPS-co-PHEMA copolymer SN ion gel and the PDMAPS/
PHEMA DN ion gel. The tensile stress-strain curves of SN and DN ion gels
The zwitterionic copolymer SN ionogels and DN ionogels were pre­
are shown in Fig. 2a and b, respectively, and the Young’s modulus (E) at
pared through UV initiated polymerization from biocompatible betaine
low strain, fracture strength (σ b) and fracture elongation (εb) of SN and
zwitterionic DMAPS and HEMA monomer in green ChCl/EG DESs. The
DN ion gels were compared in Fig. 2c and Table 1.
DMAPS and its polymer are famous for the antibacterial activity, anti-
For the PDMAPS-co-PHEMA copolymers SN ion gels, the fracture
pollution and good biocompatibility [37], and the HEMA is a raw ma­
strength (<29 kPa) and Young’s modulus (<10 kPa) were quite low, and
terial for preparing biocompatible contact lenses [38]. The copolymer
the σb and E decreased obviously with the increase of zwitterionic
SN ionogels were prepared by one-step photo-initiated polymerization
polymer content, which can be explained by the weak mechanical per­
from the DMAPS/HEMA/DES mixture with chemical cross-linker
formance of the zwitterionic PDMAPS. Compared with SN, the DN gels
PEGDMA (Fig. 1a). The DN ionogels were prepared by two-step photo­
present obvious advantages in terms of mechanical strength, elastic
polymerization, where the first step is to prepare zwitterionic polymer
modulus and elongation. For the similar monomer ratio, the DN ion gels
PDMAPS solution, and the second step is to prepare chemically
present 10–20 times increase in fracture strength and elastic modulus
cross-linked PHMA network (Fig. 1b). The DESs uniformly dissolve the
than the corresponding SN gels, and the elongation can be also improved
zwitterionic polymer PDMAPS (image in the inset) and swell the
by 2–3 times. The DN ion gels not only possess chemically cross-linked
PDMAPS/PHEM networks. Thus, highly transparent flexible zwitter­
tough PHEMA network but also ensure sufficient physical crosslinking
ionic SN and DN ionic gels were obtained (see photos in Fig. 1b).
density; while the chemical cross-linked copolymer P(DMAPS-co-
Considering the solubility of the PDMAPS in DESs and a high loading of
HEMA) in SN ion gel is weaker than PHEMA and the copolymer struc­
DESs for good conductivity, the weight fraction of DESs was maintained
ture hinders the effective electrostatic interaction of PDMAPS moieties
at 2/3 (w/w) of the total gels. A series of PDMAPS-co-PHEMA SN and
[31]. With the increase of weak physically cross-linked zwitterionic
PDMAPS/PHEMA DN ion gels were prepared by changing the monomer
PDMAPS content in the DN ion gels, the breaking strength and Young’s
ratio of DMAPS and HEMA (Table 1, note: SNx and DNx with the same x
modulus decrease to some extent, but the elongation gradually increases
were prepared from the similar DMAPS/HEMA monomer ratios), and

Fig. 1. Schematic illustration of the chemical structure, network and preparation process of (a) SN and (b) DN ion gels. Inset: corresponding photos of PDMAPS/DESs
solution and DN ion gel.

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J. Lan et al. Polymer 231 (2021) 124111

Fig. 2. Mechanical performances of SN and DN ion gels. The tensile stress-strain curves of (a) SN ion gels and (b) DN ion gels, respectively. (c) The comparison of
Young’s modulus E at low strain, fracture strength σ b and fracture elongation εb of SN ion gels and DN ion gels.

from 527% to 1033%. The physical cross-linking network plays a role as consisting of non-covalent and covalent bonds [39,40]. Compared with
a reversible sacrificial bond and thus enhances the toughness of the gel, the SN4, the DN4 presents 20 times increase in mechanical strength and
consistent with mechanical behaviors of reported hybrid DN gels 2.5 times increase in the elongation. The tensile curves of both SN and

Fig. 3. The compressive stress-strain curves of (a) DN ion gels and (b) SN ion gels, respectively. (c) Cyclic tensile behaviors of DN4 ion gel under different strains. (d)
At 200% strain, the immediate cyclic tensile behavior of DN4 ion gel and the cyclic tensile behavior after recovery for a period of time.

4
J. Lan et al.
DN ion gels at room temperature behave in an elastomeric manner and
do not show any obvious stress yielding.
The stress-strain curves of compression test for the SN and DN ion
gels further demonstrate the highly improved strength of DN ion gels
(Fig. 3a and b, Fig. S1†). Both DN and SN ion gels do not break when the
compression ratio reaches 80%, and maintain good linear viscoelasticity
under 60% strain. With the increase of zwitterionic polymer content, the
compressive strength of both DN and SN ion gels decreases gradually,
and the compressive strength of DN ion gels is much higher than that of
SN ion gels (Fig. S1†), consistent with the tensile test results.
Overall, the DN ion gels present highly improved comprehensive
mechanical performance than SN ion gels. For the DN ion gel, the
electrostatic interaction of zwitterionic PDMAPS provides a physical
cross-linking and ensures the good viscoelasticity while the chemical
cross-linked PHEMA provides the toughness and strong mechanical
performance. The unique structures of DN ion gels endow them with
excellent mechanical performance. Considering the mechanical perfor­
mance and the zwitterionic polymers content, the DN4 ion gel with high
stretchability is chosen for further characterization and application.
The energy dissipation behavior of DN4 ion gel was further investi­
gated through the loading-unloading test. Fig. 3c shows the cyclic tensile
test of DN4 ion gel at different strains. During the loading-unloading
cycle, DN4 ion gel showed obvious mechanical hysteresis. When the
strain increased from 200% to 800%, the dissipated energy increased
from 11.44 kJ m− 3 to 69.75 kJ m− 3 (Fig. S2a†). The energy dissipation
ability of DN ion gel is attributed to the physical crosslinking and in­
teractions such as hydrogen bond and electrostatic interaction. The
energy dissipation mechanism of DN ion gel is further verified from the
stress-strain curves of loading and unloading process under fixed strain
with different recovery time. As shown in Fig. 3d, with the extension of
recovery time, the DN4 gradually recovered to its initial state. In the
tensile cycle test after recovering at room temperature for 10 min, the
recovery rate of dissipated energy exceeded 90% of the initial value
(Fig. S2b†). It is proved that the physical interaction inside the DN ion
gel is partially destroyed to dissipate energy during the deformation
process, and the DN ion gel gradually returns to its initial state with the
recovery of physical interaction during the deformation recovery pro­
cess. The high stretchability, good toughness and fatigue resistance of
Fig. 4. (a) Photographs of twisted and stretched DN4 ion gels. (b) Transmittance spectra of DN4 ion gel and DN4 hydrogel in the range of 400–800 nm, and the insets
are photos of DN4 ion gel and DN4 hydrogel. (c) Current–time curve of the DN ion gel polarized at 1 V, and the inset shows the DN ion gel used as a conductor to light
a LED bulb. (d) Weight retention of the DN ion gel and hydrogel kept in an oven at 40 ◦ C. (e) DSC curves of the DN ion gel and hydrogel. (f) Tensile stress-strain
curves of the DN ion gel at − 60, − 40, − 20 and 0 ◦ C, respectively.
5
Polymer 231 (2021) 124111
DN4 ionic gel provide a broad application prospect as flexible electronic
devices.
3.2. Transparency, conductivity and low-temperature properties of DN
ion gel
The DN4 ion gel can be arbitrarily twisted and pulled up to 10 times
the initial length (Fig. 4a) while maintaining its original shape upon
stress release. The UV spectrum demonstrates a high transmittance
(>90%) for the 0.5 mm thick DN ion gel films in the whole visible
wavelength range of 400–800 nm, and the pattern behind the gel can be
clearly seen through the DN ion gel (Fig. 4b). In addition, the DN ion gel
still maintains good transparency at − 40 ◦ C (Fig. S3†). The transparency
of DN ion gel enables its application of wearable electronic devices that
require high transparency [9,41]. On the contrary, DN hydrogel pre­
pared from the same monomers is opaque. The results indicate that
PDMAPS and PHEMA are homogeneous in DESs, but the phase separa­
tion of PDMAPS and PHEMA occurs in aqueous environment. SEM
image of the DN4 ion gel shows the projected smooth texture and EDS
mapping further indicates that N, S and Cl elements are uniformly
distributed in the DN matrix (Fig. S4†), demonstrating that DESs,
PDMAPS and PHEMA are uniformly distributed throughout the DN ion
gel. In addition, the prepared DN ion gel has good conductivity and can
be used as an ionic conductor to light the LED bulb (Fig. 4c).
The stability and frost-resistance are very important to prolong the
service life and extend the operating temperature range of flexible
conductive materials [42,43]. The TGA results show that the DN ion gel
is basically stable below 100 ◦ C and starts to lose weight above 100 ◦ C,
and the obvious weight loss occurs at around 260 ◦ C. In contrast, the
obvious thermal weight loss of DN hydrogel appears below 100 ◦ C
(Fig. S5†). We further compared the stability of the DN ion gel and DN
hydrogel in an oven at 40 ◦ C. After 12 h, the water content of DN
hydrogel decreases sharply (Fig. 4d), while DN ion gel almost does not
show any weight loss, indicating the excellent low volatility and supe­
rior thermal stability.
In addition, DN ion gel has excellent frost-resistance. The freezing
point of DN hydrogel decreases slightly to − 8 ◦ C due to the presence of
ChCl salt, Fig. 4e. However, the freezing point of DN ion gel was not
J. Lan et al.
observed even dropping to − 65 ◦ C. We further studied the mechanical
properties of DN ion gel at low temperatures and the stress-strain curves
of DN4 ion gel at 0, − 20, − 40 and − 60 ◦ C were shown in Fig. 4f. At 0 and
− 20 ◦ C, the tensile curves of the DN4 ion gels still behave in an elas­
tomeric manner. At − 40 ◦ C, a stress yielding occurs, but the elongation
still reaches 400%, indicating the DN4 ion gel behaves as tough plastics.
With the decrease of temperature, the Young’s modulus E and fracture
strength gradually increase. At − 60 ◦ C, the fracture strength increase to
1 MPa and the elongation at break is still >200%. The results show that
the DN ion gel has prominent advantages in freezing resistance and can
be used at low temperature.
3.3. Electrical performance of DN ion gel
Conductivity is also an important index to evaluate the performance
of flexible conductive materials. The ionic conductivity of a series of DN
ion gels was studied in detail by EIS (Fig. 5a). The resistance is obtained
from the intercept between these curves and the real axis (inset of
Fig. 5a), and the ionic conductivity of the ion gel is calculated by the
equation σ = L/(R⋅S). It is well known that the zwitterionic polymers can
promote the dissociation of anions and cations in ionic conductive media
[31,44]. As shown in Fig. 5b and Table S3, from DN1 to DN4 ion gel, the
ionic conductivity increases from 0.281 to 0.315 S m− 1 with the increase
of the relative content of zwitterionic polymer. Similarly, with the in­
crease of zwitterionic polymer content in SN ion gels, the ionic con­
ductivity also increases obviously (Fig. S6†). The zwitterionic polymer
can improve the ionic conductivity of ion gel, and the good ionic con­
ductivity is the key factor for ion gel to be used as flexible electronic
device [45].
We further investigated the relationship between conductivity and
temperature of DN4 ion gel from − 60 to 60 ◦ C (Fig. 5c). With the in­
crease of temperature, the mobility of anion and cation of DESs in­
creases, and the ionic conductivity increases. The logarithm of ionic
Fig. 5. The electrical performances of DN ion gels. (a) EIS plots of DN ion gels with different composition at room temperature, and the inset is a partial enlargement.
(b) Electrical conductivity of different DN ion gels. (c) Arrhenius plot of conductivity for DN4 ion gel, and the inset shows the curve of conductivity of DN4 ion gel
changing with temperature. (d) Linear scanning voltammetry curve of DN4 ion gel at room temperature.
6
Polymer 231 (2021) 124111
conductivity is linear with the reciprocal of temperature, which in­
dicates that the relationship between ionic conductivity and tempera­
ture follows the typical behavior of Arrhenius [19,46]. Due to the
temperature dependence of the conductivity of DN ion gel, DN ion gel
also has the potentials in application of temperature sensors.
Furthermore, the voltage window of DN4 ion gels was studied by the
linear sweep voltammetry (LSV). The anode current is around zero
below 2.7 V, but significantly increases with the applied voltage above
2.7 V, which should be ascribed to the decomposition of DESs (Fig. 5d).
The DN ion gel can work stably in a voltage range of 0–2.7 V, which will
be of great interest in the flexible energy storage devices such as high-
capacity rechargeable Li–S, Na–S, Zn batteries or supercapacitors. In
contrast, the electrochemical window of DN hydrogel is narrow, and the
applied voltage actually allowed is less than 1.0 V (Fig. S7†).
3.4. Performance of DN ion gel as a strain sensor
The DN ion gels developed here present good tensile properties and
electrical conductivity, and also show certain advantages in trans­
parency and frost resistance, which makes DN ion gel an excellent
candidate material for assembling flexible and stretchable electronic
devices. The application potential of DN ion gel in flexible electronic
devices was demonstrated by studying the performance of DN ionic gel
as a flexible strain sensor. A simple strain sensor made from DN ion gel,
commercial adhesive tape and wire is used to detect the change of
resistance when DN ion gel is deformed, with the signal output through
the Keithley 2601B system source table. As shown in Fig. 6a and Fig. 6b,
the resistance change value (ΔR/R0) of DN ion gel shows stable strain
response in a wide range. The gauge factor (GF) is calculated by linearly
fitting the ΔR/R0-strain plot, and GF corresponds to the slope of the
linear graph (Fig. 6c), which has been usually used to evaluate the
sensitivity of the strain sensors. It can be seen that the GF is 1.49 in the
strain range 0–100%, and goes up to 2.25 in the strain range 100–500%.
J. Lan et al. Polymer 231 (2021) 124111

Fig. 6. Flexible strain sensors based on DN ion gel. The ΔR/R0 variation of DN ion gel at different strain in the range of (a) 0–100% and (b) 200–500%, respectively.
(c) The linear relationship between the ΔR/R0 variation of the DN ion gel and tensile strain. (d) The ΔR/R0 variation of DN ion gel during continuous stretch and
release from 0 to 100% strains for 150 cycles. (e) Zoomed-in image of the marked part of d. (f) Response time (Δt) of strain sensor under 50% tensile strain.

Moreover, the flexible strain sensor based on DN ion gel has excellent
reliability and mechanical durability. Fig. 6d shows the change of
relative resistance of the strain sensor during 150 cycles of 0–100%
tensile deformation. The change of relative resistance after multiple
cycles is consistent and stable, and the drift and fluctuation are small
(Fig. 6e). More importantly, the strain sensor has fast response, with a
response time as low as 200 ms (Fig. 6f).
Based on the excellent performances described above, the DN ion
gels strain sensors can be used to detect various limb movements of
human body in real time. The flexible strain sensors are applied to
several joints of human body to test its performance in monitoring large
and subtle movements of human body. As shown in Fig. 7a–c, the sensor
can clearly record the process of finger bending, slow/rapid bending of
wrist joint, and repeated bending of elbow joint, respectively. The strain

Fig. 7. Limbs movement detection by the strain sensors based on DN ion gel. The ΔR/R0 variation of the flexible strain sensors attached on the finger (a), the wrist
(b), the elbow (c), and the throat (d) during cyclic movement, and the insets are the corresponding photographs.

7
J. Lan et al.
sensor successfully captured differential signals with slight differences
in the motion of different joints. It can be seen that the peak resistance
responses of finger, wrist and elbow flexion/extension are different,
which indicates that the sensor has a high degree of differentiation for
motion monitoring. More importantly, the strain sensor can also
monitor the slight strain, such as swallowing process of human throat
(Fig. 7d). These results demonstrate that the strain sensor based on DN
ion gel can accurately detect human limb movement and movement
state, and has great application potentials in the field of human health
monitoring, diagnosis and treatment.
4. Conclusions
In this study, a kind of unique DESs-based zwitterionic DN ion gel
was proposed, which ensures high ductility and excellent fatigue resis­
tance, as well as high transparency, high ionic conductivity, good sta­
bility and frost-resistance. The advantages of double-network ion gels in
mechanical and conductive performances compared with that of
copolymer single network gel were described. More importantly, the
main components of the zwitterionic DN ion gel are non-toxic and
biocompatible, thus the prepared DN ion gel is a green and environment-
friendly flexible conductive material. As a strain sensor, DN ion gel
shows advanced characteristics such as fast response speed, high sensi­
tivity and good durability, which can be used for human health moni­
toring in a wide temperature range. This work provides a new concept
for the preparation of green flexible conductive materials with excellent
comprehensive properties and multi-functions.
CRediT authorship contribution statement
Ji Lan: Methodology, Validation, Investigation, Data curation,
Writing – original draft. Bo Zhou: Methodology, Validation, Investiga­
tion, Data curation. Chenxiao Yin: Methodology, Validation, Investi­
gation, Data curation. Lin Weng: Methodology, Validation,
Investigation, Data curation. Wei Ni: Methodology, Formal analysis,
Investigation, Writing – review & editing. Ling-Ying Shi: Conceptuali­
zation, Methodology, Investigation, Supervision, Resources, Validation,
Formal analysis, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
Financial support from the National Natural Science Foundation of
China (Grant 51403132), the Applied Basic Research Program of Science
and Technology Commission Foundation of Sichuan Province (Grants
2021YJ0559), and the Fundamental Research Funds for Central Uni­
versities are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2021.124111.
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