Energy Storage Materials 41 (2021) 599–605

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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Flexible and anti-freezing zinc-ion batteries using a

guar-gum/sodium-alginate/ethylene-glycol hydrogel electrolyte
Jiawei Wang a, Yuan Huang b,∗, Binbin Liu a, Zixuan Li a, Jiyan Zhang a, Guoshen Yang a,
Pritesh Hiralal c, Shunyu Jin d, Hang Zhou a,∗
a
School of Electronic and Computer Engineering, Peking University Shenzhen Graduate School, Shenzhen, 518055, PR China
b
School of Microelectronics Science and Technology, Sun Yat-Sen University, Guangzhou, PR China
c
Zinergy Shenzhen Ltd., Floor 6, Building H, Gangzhilong Science Park, Longhua, Shenzhen, PR China, 518109
d
Center for Micro- and Nanoscale Research and Fabrication, University of Science and Technology of China, Hefei, 23000, PR China

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

Keywords: Natural polymer hydrogels are promising candidates for solid-state electrolytes in zinc-ion batteries. They are safe,
Natural polymers biocompatible, and mechanically robust. However, the ionic conductivity of most natural polymer-based hydro-
Hydrogel gels is unsatisfactory, and they are particularly problematic at sub-zero temperatures because freezing severely
Ionic conductivity
limits their functionality. In this study, we fabricate composite hydrogels with high ionic conductivity (25.37 mS
Anti-freezing
cm−1 ). This is done by blending two kinds of natural polymers, guar gum (GG) and sodium alginate (SA). The
Zinc-ion batteries
Low temperature zinc-ion batteries with GG/SA hydrogel electrolytes show a superior electrochemical performance (354.9 mAh
g−1 at 0.15 A g−1 , 137.0 mAh g−1 at 6 A g−1 and capacity retention of 91.52% over 1000 cycles) than the zinc-ion
batteries with the pure GG hydrogel electrolyte. In addition, to extend the application range of GG/SA hydrogels
into the sub-zero temperature region, we introduce ethylene glycol (EG) into GG/SA to form GG/SA/EG anti-
freeze hydrogel. Below -20 °C, the GG/SA/EG hydrogel maintains a high ionic-conductivity (6.19 mS cm−1 ), and
the zinc-ion batteries, which were made of GG/SA/EG hydrogel electrolyte, showed an excellent low-temperature
discharge performance, for a specific capacity of 181.5 mAh g−1 at 0.1 A g−1 . This study describes a new approach
for the development of natural polymer-based hydrogel electrolytes with high ionic-conductivity and good anti-
freeze capability.

1. Introduction
Aqueous zinc-ion batteries (ZIBs) have attracted worldwide atten-
tion due to their environmentally friendly composition, high theoreti-
cal capacity (820 mAh g−1 and 5855 mAh cm−3 ), low redox potential
(−0.76 V vs. standard hydrogen electrode), and the abundance of Zn
on Earth (~300 times higher than lithium) [1–4]. Liu et al. ascribed
the capacity fading of Zn-MnO2 batteries with ZnSO4 electrolyte to the
Mn dissolution from the MnO2 electrode. They suppressed Mn dissolu-
tion into the electrolyte from the electrode and increased the stability of
aqueous Zn-MnO2 batteries substantially by adding a specific amount of
MnSO4 salt to the ZnSO4 aqueous electrolyte, which greatly accelerated
the development of ZIBs [5]. However, aqueous ZIBs still suffer from
electrolyte leakage, dendrite formation, and the inevitable corrosion of
Zn anodes in any aqueous electrolyte [6]. As a result, many studies were
done to further develop solid-state electrolytes. For example, Chen et al.
used cotton as raw material and tetraethyl orthosilicate as crosslinking
agent to prepare a hydrogel electrolyte for ZIBs. This resulted in envi-
ronmentally friendly and dendrite‐free batteries [7]. Wang et al. pre-
pared solid-state electrolyte by coupling the grafted copolymer xanthan
gum-polyacrylamide with cotton cellulose nanofiber. This produced a
material with high ionic-conductivity, good adhesion, high mechanical
strength, strong ion-adsorption and an inhibition effect with respect to
the generation of dendrites [8].
Among reported solid-state electrolytes, hydrogels, which are based
on natural polymers have been well studied and developed because they
are safe, biocompatible, and abundant on Earth. Pure natural polymer-
based hydrogels, such as guar gum (GG) hydrogel [9], xanthan gum hy-
drogel [10] and carrageenan hydrogel [11] were already used as reser-
voirs for aqueous ZnSO4 + MnSO4 electrolyte. In our previous study,
we showed that GG is soluble in water, salt tolerant, and has high acid
resistance, which render it an ideal candidate for solid state electrolyte
[9]. Unfortunately, the ionic conductivity of pure GG hydrogels is un-
satisfactory, and the hydrogels, inevitably, freeze and become noncon-
ductive at sub-zero temperatures. This is a big problem for applications.
Commonly, introducing the common antifreeze such as ethylene glycol
(EG) improves the anti-freezing properties of the hydrogels, because the

∗
Corresponding author.
E-mail addresses: huangy723@mail.sysu.edu.cn (Y. Huang), zhouh81@pkusz.edu.cn (H. Zhou).

https://doi.org/10.1016/j.ensm.2021.06.034
Received 2 April 2021; Received in revised form 13 June 2021; Accepted 22 June 2021
Available online 5 July 2021
2405-8297/© 2021 Elsevier B.V. All rights reserved.
J. Wang, Y. Huang, B. Liu et al.
abundance of hydrogen bonds in the water and EG mixture disrupts the
formation of crystal lattices of ice [12,13].However, the ionic conduc-
tivity of the resulting hydrogels containing EG is reduced due to the
decrease in water content [13], leading to the inferior electrochemi-
cal performance at room temperature. Hence, the challenge remains to
develop lost-cost natural polymer-based hydrogel electrolytes for ZIBs
with high ionic conductivity and anti-freezing properties.
One way to tackle this challenge is to blend other polymers to con-
struct crosslinked composite-hydrogels with better properties than pure
natural polymer-based hydrogels. Sodium alginate (SA), which con-
sists of two monomeric units, 𝛽-D-mannuronic acid (M-block), and 𝛼-
L-guluronic-acid (G-block), are widely used to create composite materi-
als because of their biocompatibility, good forming-properties, and low
cost [14]. The abundant hydrophilic functional hydroxyl and carboxylic
groups on the polymer chains can facilitate both Zn-salt absorption and
dissociation [15]. In addition, the carboxylic groups are uniformly dis-
tributed in the polymer chain, which could be conductive to the trans-
port of ions [16]. These attractive features inspire us to introduce SA
into pure GG hydrogel or the corresponding hydrogels containing EG
for further improving the ionic conductivity of the hydrogels and elec-
trochemical performance of the batteries.
In this study, we prepared a composite hydrogel (denoted as GG/SA)
with high ionic conductivity (25.37 mS cm−1 , note that the ionic con-
ductivity of the aqueous electrolyte 2 M ZnSO4 + 0.1 M MnSO4 is 48 mS
cm−1 [9]) and excellent flexibility. This was done by blending two kinds
of natural polymers, GG and SA. The ZIBs with GG/SA hydrogel showed
an enhanced electrochemical performance (354.9 mAh g−1 at 0.15 A
g−1 , 137.0 mAh g−1 at 6 A g−1 ) compared with pure GG hydrogel
(258.6 mAh g−1 at 0.15 A g−1 , 103.8 mAh g−1 at 6 A g−1 ) at 25 °C.
Moreover, we show that, by introducing EG into the GG/SA hydrogels
via a solvent-displacement-induced toughening (SDIT) method, the en-
hanced anti-freezing property of the hydrogel (denoted as GG/SA/EG)
can be accomplished. It reaches a high ionic conductivity of 6.19 mS
cm−1 at −20 °C. Overall, the ZIBs with GG/SA/EG hydrogel electrolyte
maintained a high specific capacity (181.5 mAh g−1 at 0.1 A g−1 ) as
well as an excellent cycling performance (80.39% capacity retention
over 100 cycles at 0.3 A g−1 ) below −20 °C.
2. Experimental
2.1. Materials
Sodium alginate (SA, AR, >99%), Guar gum (GG, AR, >99%), Ethy-
lene glycol (EG, Standard for GC, ≥99.5%) and ZnSO4 •7H2 O (ACS, 99%)
were purchased from Aladdin Chemical Reagent Co., Ltd., while MnSO4
(AR, >99%) was purchased from Macklin Chemical Reagent Co., Ltd..
2.2. Preparation of the GG/SA and the GG/SA /EG hydrogel electrolytes
The GG/SA hydrogel electrolyte was synthesized using a one-pot
method modified based on our previous report [9]. Typically, 0.4 g
SA and 0.2 g GG were stirred together in a beaker. Then, 10 ml of
2 M ZnSO4 + 0.1 M MnSO4 electrolyte solution was poured in and
stirred continuously at room temperature for 30 min. Finally, the ho-
mogeneously mixed hydrogel electrolyte was transferred to a Petri dish
and left standing for 24 h to produce a GG/SA hydrogel electrolyte with
good flexibility.
The GG/SA/EG hydrogel electrolyte was obtained by immersing the
prepared GG/SA hydrogel electrolyte in a 30% volume EG solution of
2 M ZnSO4 + 0.1 M MnSO4 for 24 h.
2.3. Characterization of the structure and morphology
A field-emission scanning electron microscope (FESEM, Carl Zeiss
SUPRA-55) was employed to determine the morphology of the surface.
A Fourier transform infrared spectrometer (FTIR, Bruker Vertex-70) was
600
Energy Storage Materials 41 (2021) 599–605
used to characterize the samples. TGA was performed by using a simul-
taneous thermal analyser (MDTC-EQ-M05-01).
2.4. Electrochemical characterization
Electrochemical impedance spectroscopy (EIS), linear scanning
voltammetry (LSV), corrosion tests and cyclic voltammetry (CV) were
conducted using an electrochemical workstation (CHI 660E, Shanghai
Chenhua Instrument Co., Ltd.). The electrochemical tests at different
temperatures were carried out at constant temperature in a humidity
chamber (RHP-23, REALE).
The ionic conductivity 𝜎 (mS cm−1 ) of the electrolytes was measured
using EIS (0.01 Hz to 10k Hz). A piece of the prepared hydrogel elec-
trolyte was placed between two stainless sheets. The conductivity 𝜎 was
calculated according to 𝜎 =L/(R•A), where L (cm), A (cm2 ), and R (Ω)
are the thickness, electrode contact area, and bulk resistance, which
were determined by the intercept with the x-axis in Nyquist plots, re-
spectively. LSV measurements were carried out using SS as working elec-
trode and a Zn plate as reference and counter electrodes. The corrosion
potential and current of the samples were derived from Tafel fit plots in
a three electrodes configuration, where the Zn plate was used as work-
ing electrode, the Ag/AgCl electrode as reference electrodes, the Pt plate
as counter electrode. CV curves of Zn plating/stripping were measured
using a three-electrode configuration, where SS was used as working
electrode and the Zn plates as reference and counter electrodes.
To prepare the MnO2 /Super P/PVDF cathode, 70 wt.% of the 𝛼-
MnO2 powder (prepared using a hydrothermal method [17]), 20 wt.%
of Super P (SP) and 10 wt.% of polyvinylidene fluoride (PVDF) were
mixed in N-Methyl pyrrolidone (NMP) for 4 h using a magnetic stirrer.
Then, the slurry was coated on the carbon cloth and dried at 70 °C for
6 h. The electrode area was about 1.54 cm2 , and the mass loading of the
active material was 1.5–2 mg cm−2 .
Galvanostatic charge-discharge (GCD) measurements were per-
formed using a Land CT2001A battery-test system (Wuhan Land Elec-
tronic Co., Ltd).
Symmetric cells were assembled to assess the stability of the GG,
GG/SA, and GG/SA/EG hydrogel electrolytes. In symmetric Zn|Zn cells,
two identical bare Zn foils, with a diameter of 14 mm, were used as
negative and positive electrodes. Long-term cycling stability was mea-
sured from 0.2 mA cm−2 to 2 mA cm−2 at different temperatures. Fur-
thermore, based on the MnO2 /Super P/PVDF cathode and Zn foil an-
ode, the electrochemical properties of ZIBs with hydrogel electrolytes
were determined. CV curves were conducted at 0.1 mV s−1 from 1.0 to
1.9 V vs. Zn2+ /Zn. EIS plots of ZIBs were carried out from 100k Hz to
0.01 Hz. The GCD performance of the battery was tested by varying the
charge/discharge current density at different temperatures. Finally, in
the bending test section, the zinc foil anode was replaced with a zinc
plated anode (constant-current plating method [18]).
3. Results and discussion
The synthesis of the GG/SA hydrogel, which was prepared by mixing
GG and SA in ZnSO4 + MnSO4 aqueous solution (followed by the solid-
ification), produced a solidified gel consisting of a GG-SA cross-linked
network. Using an SDIT method, the as-prepared GG/SA hydrogels were
simply soaked with a mixture of EG and ZnSO4 /MnSO4 solution. This
was done to obtain the GG/SA/EG hydrogel during the exchange of wa-
ter in the gel network with EG in the soaking solution (see Experimen-
tal Section and Fig. 1a for details). EG acted as an anti-freezing agent
to maintain the mechanical and electronic properties of the GG/SA/EG
hydrogels over a wide temperature-range [12,13,19]. In the GG/SA/EG
hydrogel, the EG forms stable molecular clusters with H2 O molecules
that compete with hydrogen bonds in water. This resulted in a decrease
of saturated vapor pressure of water. As a result, the formation of the
crystal lattice of ice was disrupted, and the freezing point was lowered
[12]. The amount of all components in the GG/SA/EG hydrogel was
J. Wang, Y. Huang, B. Liu et al.
evaluated and presented in Supporting Information (Fig. S1 and Table
S1). The pure guar gum hydrogel (denoted as GG hydrogel) electrolyte
can be obtained by mixing the GG with the ZnSO4 + MnSO4 aqueous
solution. However, pure SA cannot be converted into a hydrogel using
the above method, which is too fragile to be used in batteries. Therefore,
GG was used here to enhance the mechanical strength of both GG/SA
and GG/SA/EG hydrogels.
The morphology of GG, GG/SA, and GG/SA/EG hydrogel electrolytes
was investigated using SEM. As shown in Fig. 1b, there were some
cracks on the surface of the GG hydrogel. For comparison, the GG/SA
and GG/SA/EG hydrogels featured interconnected porous structures and
dense wrinkles (Fig. 1c-d). Optical images of GG, GG/SA, and GG/SA/EG
hydrogel electrolytes are shown in Fig. 2e-g. All of them showed a
translucent state. The GG sample was yellowish, while the GG/SA color
became lighter after the addition of SA. The GG/SA/EG sample showed
a more transparent state because it included EG in the polymer network.
To investigate their anti-freezing properties, the samples were stored in
−20 °C for 2 h. Both the GG and GG/SA samples froze (Fig. 1h-i), while
the GG/SA/EG sample retained the hydrogel state due to the existence
of EG (Fig. 1j). The results confirm the expected excellent anti-freezing
capability of the GG/SA/EG samples. We also test the flexibility of the
GG, GG/SA, and GG/SA/EG hydrogels. All of the hydrogels sustained
various large deformations of twisting at room temperature (Fig. S2).
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Energy Storage Materials 41 (2021) 599–605
Fig. 1. (a) Schematic illustration of the fabri-
cation of GG/SA and GG/SA/EG hydrogel elec-
trolytes. SEM images of (b) GG, (c) GG/SA, and
(d) GG/SA/EG hydrogel electrolytes. Optical
images of (e) GG, (f) GG/SA, and (g) GG/SA/EG
hydrogel electrolytes at 25 °C. Optical images
of (h) GG, (i) GG/SA, and (j) GG/SA/EG hydro-
gel electrolytes at −20 °C.
Fig. 2. (a) Comparison of the ionic conduc-
tivity of GG, GG/SA, and GG/SA/EG hydro-
gel electrolytes at 25 °C and −20 °C. (b) LSV
curves and (c) Tafel plots of the GG, GG/SA,
and GG/SA/EG hydrogels. (d) The CV curves
of Zn-plating/stripping in the GG, GG/SA, and
GG/SA/EG hydrogels. (e) Cycling performance
of the Zn/Zn symmetrical cell with the GG,
GG/SA, and GG/SA/EG hydrogels for 0.2 mA
cm−2 at 25 °C. (f) Voltage profiles of the Zn/Zn
symmetrical cell with the GG, GG/SA, and
GG/SA/EG hydrogels for different current den-
sities at 25 °C. (g) Voltage profile of the Zn/Zn
symmetrical cell with the GG/SA/EG hydrogel
at 0.2 mA cm−2 for different temperatures. (h)
Cycling performance of the Zn/Zn symmetrical
cell with the GG/SA/EG hydrogels and 0.2 mA
cm−2 at 0 °C and −20 °C.
The GG and GG/SA hydrogels were frozen into solid ice at −20 °C and
broken when large twisting was imposed. In contrast, the GG/SA/EG
hydrogel retained the hydrogel state and its mechanical properties were
well preserved, exhibiting high elasticity to sustain various large defor-
mations of twisting at −20 °C.
The FTIR spectra of the GG, GG/SA, and GG/SA/EG hydrogel elec-
trolyte as well as pure SA powder were collected and are shown in Fig.
S3. For the GG hydrogel, the bands at approximately 3232 cm−1 are re-
lated to O–H stretching vibrations of hydrogen bonds [9,20]. Moreover,
the bands at 1644 cm−1 and 1072 cm−1 are attributed to both O–C-O
asymmetric vibrations and C–O-C asymmetric vibrations [9,21–23]. For
the GG/SA and GG/SA/EG hydrogel, these similar characteristic peaks
also appear, which confirms the presence of guar gum. In addition, there
are other absorption peaks at 1424 cm−1 and 1420 cm−1 in the FTIR
spectra of the GG/SA and GG/SA/EG hydrogel. They originate from SA,
which also appears in the FTIR of the pure SA powder at 1408 cm−1 .
This absorption peak is attributed to asymmetric symmetric stretching
vibrations of the -COO- groups on the SA chains [15,23,24]. Accord-
ing to several studies [25,26], the bands at 1068 cm−1 and 1032 cm−1
in the FTIR spectrum of GG/SA/EG hydrogel can be attributed to C–O
stretching vibration of epoxy and alkoxy groups of EG.
The ionic conductivity of the hydrogel electrolyte was determined
from the AC impedance spectra, and the results are shown in Fig. 2a.
J. Wang, Y. Huang, B. Liu et al.
At 25 °C, the ionic conductivity of GG and GG/SA hydrogel electrolytes
reached 10.24 and 25.37 mS cm−1 , respectively. This indicates that the
introduction of SA can increase the ionic conductivity of the hydrogel
electrolyte at room temperature. In comparison, the ionic conductivity
of GG/SA/EG (16.81 mS cm−1 ) was lower than for GG/SA at 25 °C.
This is due to the decrease in water content of the hydrogels [13]. Nev-
ertheless, the GG/SA/EG hydrogel electrolyte maintained a high ionic
conductivity of 6.19 mS cm−1 , while both the GG and GG/SA hydro-
gel froze at −20 °C. This indicates that, although the introduction of EG
decreased the ionic conductivity of the hydrogel, the presence of the
EG helped lower the freezing point of the GG/SA/EG hydrogel. This is
due to the large number of hydrogen bonds between the water and EG,
which disrupts the formation of crystal lattices of ice [12]. However, it
is worth noting that the ionic conductivity of the resulting GG/EG hy-
drogel is 7.62 mS cm−1 at 25 °C and only 1.39 mS cm−1 at −20 °C (Fig.
S4). The lower conductivity of the resulting GG/EG hydrogel is due to
the decrease in water content [13].
Furthermore, the electrochemical properties of GG, GG/SA, and
GG/SA/EG hydrogel electrolytes were verified. As shown in Fig. 2b,
the GG, GG/SA, and GG/SA/EG showed high electrochemical stability-
windows of 2.33 V, 2.31 V, and 2.27 V, respectively. The electrochem-
ical stability windows were high enough for almost all aqueous Zn bat-
tery systems [27].
Potentiodynamic polarization tests were used to measure the cor-
rosion of the Zn plate emerged in electrolytes. Both the corrosion po-
tential and current of the samples were derived from the Tafel fit plots
in Fig. 2c. The more positive corrosion-potential and the lower corro-
sion current indicate a smaller tendency for a corrosion reaction and
the lower corrosion rate, respectively. This is usually due to hydrogen
evolution and dissolved oxygen passivation [6]. Clearly, the corrosion
potentials of the GG (−0.982 V), GG/SA (−0.984 V), and GG/SA/EG
(−0.981 V) samples were very similar. In addition, the corrosion cur-
rents for GG/SA (0.2133 mA cm−2 ) and GG/SA/EG (0.2939 mA cm−2 )
hydrogel were much lower than for GG hydrogel (0.7398 mA cm−2 ).
Thus, GG/SA and GG/SA/EG hydrogel electrolyte appear to be less
corrosive for zinc foil compared with the GG hydrogel. The Zn plat-
ing/stripping behavior in these hydrogel electrolytes was investigated
using a CV test (Fig. 2d). Moreover, Zn2+ begins to be reduced to Zn on
the substrate at −0.152, −0.145 and −0.154 V, while metallic Zn is dis-
solved at 0.258, 0.252, and 0.249 V in the GG, GG/SA, and GG/SA/EG
hydrogels. The highest current-density was observed in the CV curve
of GG/SA hydrogel, which shows faster kinetics in the GG/SA hydrogel
[23,28].
The long-term cycling property of the symmetric Zn cells with GG,
GG/SA, and GG/SA/EG hydrogel electrolytes at 25 °C are shown in
Fig. 2e. For a current density of 0.2 mA cm−2 , the cells with GG/SA
and GG/SA/EG showed stable voltage profile over 100 cycles, while the
polarization voltage of the cell with GG increased during the cycling pro-
cess. Then, the polarization voltage of Zn plating/stripping was investi-
gated for different current densities from 0.1 to 2.0 mA cm−2 (Fig. 2f).
When the current-density increased from 0.1 mA cm−2 to 2.0 mA cm−2 ,
the polarization voltages of the symmetric Zn cells with GG/SA and
GG/SA/EG hydrogels were always below 200 mV. However, a sudden
increase in polarization was observed in symmetric cells with GG hy-
drogel electrolyte, when the current density increased to 2.0 mA cm−2 .
This indicates that the GG/SA and GG/SA/EG hydrogel electrolyte are
more promising candidates for ZIBs for a wide range of current densities
than the GG hydrogel electrolyte. As mentioned earlier, the GG/SA/EG
hydrogel features excellent anti-freezing properties, thus we investigate
the polarization voltage for Zn plating/stripping of the symmetric Zn
cells with the GG/SA/EG hydrogel electrolytes at different tempera-
tures. As shown in Fig. 3g, when the current density was 0.2 mA cm−2 ,
the polarization voltage was below ~200 mV at 25 and 0 °C. Even at
−20 °C, the polarization voltage was merely ~320 mV. The long-term
cycling properties of the symmetric Zn cells with GG/SA/EG hydrogel
at 0 °C and −20 °C are shown in Fig. 2h. The symmetric Zn cell with
602
Energy Storage Materials 41 (2021) 599–605
GG/SA/EG hydrogel electrolyte exhibited a stable cycle performance
exceeding 200 h under 0.2 mA cm−2 at 0 °C and −20 °C.
ZIBs with an MnO2 cathode and zinc-foil anode were assembled to
further evaluate the practical application of GG, GG/SA, and GG/SA/EG
hydrogel electrolyte. As shown in Fig. 3a, all the ZIBs feature a single
anodic peak and two cathodic peaks in the CV curves. The ZIBs with
GG/SA hydrogel electrolyte had the sharpest and highest peaks with
the smallest potential intervals of all the ZIBs. This indicates the low-
est polarization. Fig. 3b shows the discharging profiles for ZIBs with
GG, GG/SA and GG/SA/EG hydrogel electrolytes at a current density of
0.3 A g−1 . All of them show two similar discharging plateaus, which can
be attributed to a subsequent H+ and Zn2+ insertion process [18]. The
ZIBs with GG/SA hydrogel electrolytes had the highest specific capacity
(based on MnO2 wt) of 295.0 mA h g−1 , while the ZIBs with GG/SA/EG
and GG hydrogel electrolytes had capacities of only 261.5 and 235.0 mA
hg−1 , respectively.
Fig. 3c shows the rate performance of ZIBs with GG, GG/SA, and
GG/SA/EG hydrogel electrolytes. The ZIBs with GG/SA hydrogel elec-
trolytes show the best rate of all the ZIBs. For example, the ZIBs with
GG/SA hydrogel electrolytes had a discharge capacity of 354.9 mA h
g−1 at a low current-density of 0.15 A g−1 . When the discharge-current
density increased to higher values such as 3 and 6 A g−1 , the dis-
charge capacities were maintained at 159.9 and 137.0 mA h g−1 , re-
spectively. comparison, the ZIBs with GG/SA/EG hydrogel electrolytes
exhibited a much lower discharge capacity (~135.0 mA h g−1 at 3 A
g−1 and 90.3 mA h g−1 at 6 A g−1 ). The ZIBs with GG hydrogel elec-
trolytes had the worst rate performance. The energy and power den-
sities of ZIBs with GG, GG/SA, and GG/SA/EG hydrogel electrolytes
are compared in Fig. 3d. Furthermore, the ZIBs with GG/SA hydro-
gel electrolytes showed the highest energy-density (based on MnO2 wt),
481.0 Wh kg−1 at 0.211 kW kg−1 , and still maintained a relatively
high value of 182.6 Wh kg−1 with a large power density of 8.016 kW
kg−1 . The ZIBs with GG/SA/EG hydrogels had a lower energy-density
(432.2 Wh kg−1 at 0.208 kW kg−1 and 111.4 Wh kg−1 ) with a power
density of 7.430 kW kg−1 . Furthermore, the cycling performances of the
ZIBs with GG, GG/SA, and GG/SA/EG hydrogel electrolytes were also
determined. Again, the ZIBs with GG/SA hydrogel electrolytes had the
highest capacity retentions (91.52% after 1000 cycles at 6 A g−1 ), while
the capacity retention of the ZIBs with GG and GG/SA/EG hydrogel elec-
trolytes were only 86.22% and 78.39%, respectively (Fig. 3e).
We also evaluated the cold tolerance of the ZIBs with GG, GG/SA
and GG/SA/EG hydrogel electrolytes in more detail. The experimental
results of the ZIBs cycled sequentially at 25, 0 and −20 °C, are shown
in Fig. 3f. For the ZIBs with GG and GG/SA hydrogel electrolytes, the
degraded capacities upon cooling were obtained in such a way that the
battery retained only 37.5% and 63.4% capacity retention at 0 °C. More-
over, both of them could not operate at −20 °C. Conversely, when the
temperature dropped from 25 °C to 0 °C and −20 °C, the capacities re-
tention of the ZIBs with GG/SA/EG hydrogel electrolytes were 71.4%
(195.6 mA h g−1 ) at 0 °C and 41.5% (113.8 mA h g−1 ) at −20 °C com-
pared to the one delivered at 25 °C. When the temperature increased to
25 °C again, the specific capacity of the ZIBs with GG/SA/EG hydrogel
electrolytes was almost restored to the pristine value.
To further verify the anti-freezing capability of the ZIBs with
GG/SA/EG hydrogel electrolytes, the rate performance at −20 °C was
also measured by increasing the current density from 0.1 to 0.5 A g−1
gradually (Fig. 3g and Fig. S5). Specifically, the discharge capacities
were 181.5, 131.6, 119.6, and 106.1 mA h g−1 at 0.1, 0.2, 0.3 and 0.5 A
g−1 . When the current density returned to 0.1 A g−1 , the capacity could
reach 172.1 mA h g−1 . The ZIBs with the GG/SA/EG hydrogel electrolyte
had an energy density of 233.6 Wh kg−1 at 0.133 kW kg−1 and 141.0 Wh
kg−1 at 0.665 kW kg−1 at −20 °C (Fig. S6). In addition, the cycling per-
formance of the ZIBs with GG/SA/EG hydrogel electrolytes at −20 °C
was also measured. The capacities after 50, 100, and 150 cycles were
103.82, 92.13, and 78.28 mAh g−1 (Fig. S7). Compared to the initial
capacity of 114.61 mAh g−1 , the capacity retention after 50, 100, and
J. Wang, Y. Huang, B. Liu et al.
150 cycles was 90.59, 80.39, and 68.30% respectively. Furthermore, the
ZIBs with GG/SA/EG hydrogel electrolytes were capable of powering a
thermo-hygrometer at −20 °C, guaranteeing its practical applications
(Fig. 3h and Video S1).
Based on these results, it can be concluded that the incorporation
of SA in the hydrogel electrolyte indeed improves the electrochemi-
cal properties of the ZIBs at room temperature, which enables a high
specific-capacity, excellent rate performance, and superior cycling per-
formance. This enhancement is attributed to the following reasons. (i)
The abundant hydrophilic functional hydroxyl and carboxylate groups
of SA improve the water retention capacity of the GG/SA hydrogels
[29,30]. As show in Fig. S3, the absorption peak at 1424 cm−1 in the
FTIR spectra of the GG/SA hydrogel originates from SA, which also ap-
pears in the FTIR of the pure SA powder at 1408 cm−1 . This absorp-
tion peak is attributed to asymmetric symmetric stretching vibrations
of the carboxylate groups [15,23,24]. Fig. S8 shows the comparison of
water retention capacity of GG and GG/SA hydrogels. In a constant tem-
perature and humidity environment of 168 h, the GG/SA hydrogel has
higher water retention than the GG hydrogel. This indicates the addi-
tion of SA improves the water retention capacity of the GG/SA hydro-
gels (Fig. S8), which is attributed to the interaction between the -OH
groups of GG and the -COOH groups of SA [29]. (ii) The addition of SA
improves the ionic conductivity of the GG/SA hydrogels. The ionic con-
ductivities of GG and GG/SA hydrogels were 10.24 and 25.37 mS cm−1 ,
respectively. The ionic conductivity of hydrogels depends markedly on
the water content [31]. The superior water retention capability of the
GG/SA hydrogels greatly contributes to higher ionic conductivity of the
GG/SA hydrogels because the loss of water deteriorates the ionic con-
ductivity. (iii) Relative to the GG hydrogel, the GG/SA hydrogel behaves
faster kinetics of Zn dissolution/deposition. The Zn plating/stripping be-
havior of the GG and GG/SA hydrogels was investigated and shown in
Fig. 2d. Higher current density can be seen on the Zn plating/stripping
behavior of the GG/SA hydrogels, which assists a faster kinetics of Zn
603
Energy Storage Materials 41 (2021) 599–605
Fig. 3. (a) CV curves, (b) discharging pro-
files, (c) rate performances, (d) Ragone plots,
and (e) cycling performances of ZIBs with GG,
GG/SA, and GG/SA/EG hydrogel electrolytes
at 25 °C. (f) Discharge capacities of ZIBs with
GG, GG/SA, and GG/SA/EG hydrogel elec-
trolytes at 25, 0 and −20 °C. (g) Rate perfor-
mance of ZIBs with GG/SA/EG hydrogel elec-
trolytes at −20 °C. The ZIBs with GG/SA/EG
hydrogel electrolytes can operate at (h) 25 °C
and (i) −20 °C.
dissolution/deposition [28]. (iv) The ZIBs with the GG/SA hydrogels
has smaller internal impedance than those with the GG hydrogels. EIS
is employed to find out the electrode impedance associated with the two
samples and the corresponding Nyquist plots are shown in Fig. S9. An
appropriate equivalent-circuit model was established to fit the Nyquist
curves. As shown in Table S2, the charge transfer resistance (Rct ) of the
ZIBs with the GG/SA hydrogel is much smaller that of the ZIBs with
the GG hydrogel. This is attributed to higher ionic conductivity of the
GG/SA hydrogels.
It is also worth noting that the ionic conductivity of the GG/SA hy-
drogel electrolyte, and the electrochemical properties of the ZIBs with
GG/SA hydrogel electrolyte are fairly sensitive to the mass ratio of SA to
GG. Within a certain range, the ionic conductivity of the GG/SA hydro-
gel shows an increasing trend, when the mass ratio of SA to GG increases
(Fig. S10). This is attributed to the high number of hydroxyl and car-
boxyl groups of SA, which are hydrophilic and facilitate rapid ion mi-
gration [15,21,23,32]. The ionic conductivity of the GG/SA hydrogel
reached an optimum of 25.37 mS cm−1 , when the mass ratio of GG to
SA reached 1:2. The corresponding ZIBs show the best rate performance
and cycling performance (Fig. S11-S12).
On the other hand, as the introduction of EG decreased the ionic con-
ductivity of the hydrogel, the electrochemical performance of the ZIBs
with GG/SA/EG hydrogel electrolyte was inferior to that of the ZIBs
with GG/SA hydrogel electrolyte at room temperature. However, due
to the presence of the anti-freezing agent EG, the freezing point of the
GG/SA/EG hydrogel was lowered. In addition, the ZIBs with GG/SA/EG
hydrogel electrolyte showed superior electrochemical performance com-
pared to the ZIBs with GG/SA hydrogel electrolyte at sub-zero temper-
ature. We systematically evaluated the effect of the SDIT on the ionic
conductivity of the GG/SA/EG hydrogel electrolyte. First, the soaking
time was varied from 2 h to 48 h to investigate the ionic conductivity of
the GG/SA/EG hydrogel. As shown in Fig. S13, the ionic conductivity
of GG/SA/EG hydrogel at 25 °C and −20 °C increased for soaking times
J. Wang, Y. Huang, B. Liu et al.
between 2 h and 24 h. After 24 h soaking, the ion conductivity remained
nearly unchanged due to a saturated and stable state of the GG/SA/EG
hydrogel. The corresponding ZIBs used the GG/SA/EG hydrogel with
24 h soaking time in EG solution showed the highest specific capacities
at 25, 0, −20 °C (Fig. S14). Furthermore, the EG volume ratio in the soak-
ing solution was investigated. When the volume ratio of EG increased
from 0.1 to 0.8, the hydrogel (after soaking for 24 h) showed reduced
ion conductivity at 25 °C. However, the maximum ion conductivity at
−20 °C could be increased to 6.19 mS cm−1 using an EG volume ratio
of 0.3 (Fig. S15). In terms of electrochemical performance at 25 °C (Fig.
S16), the specific capacities of the ZIBs with GG/SA/EG hydrogel elec-
trolyte with an EG volume ratio of 0.1 was similar to that of the ZIBs
with GG/SA/EG hydrogel electrolyte with an EG volume ratio of 0.3.
However, at −20 °C, the ZIBs with the GG/SA/EG hydrogel electrolyte
with an EG volume ratio of 0.3 had higher specific capacities than the
ZIBs with GG/SA/EG hydrogel electrolyte with an EG volume ratio of
0.1. In summary, we identified a soaking time of 24 h and an EG volume
ratio of 0.3 as optimal experimental parameters.
The bendability capability is crucial for the preparation of flexible
energy-storage devices. In Fig. 4a, we assembled flexible solid-state ZIBs
with the GG/SA/EG hydrogel electrolyte (where electroplated zinc on
carbon clothe was used as anodes. For details see the Experimental Sec-
tion). Fig. 4b shows the flexible solid-state ZIBs with the GG/SA/EG hy-
drogel electrolyte powering/lighting the thermo-hygrometer under both
normal and bending conditions. After 100 and 1000 bending cycles,
with a bending radius of 10 mm, the ZIBs with GG/SA/EG hydrogel
electrolyte had a capacity of 289.8 and 234.1 mAh g−1 at 0.3 A g−1
(Fig. 4c). The corresponding capacity retention was 98.4% and 79.5%,
compared to the initial capacity of 294.4 mAh g−1 . The ZIBs with the
GG/SA/EG hydrogel also can be bent (a radius of 10 mm) without dete-
riorating the charge and discharge profile at 25 °C and −20 °C (Fig. S17).
They maintained 96.85% at 25 °C and 97.58% −20 °C of their original
specific capacities when they were at bending state, respectively. The
results demonstrate the excellent flexibility of the ZIBs with GG/SA/EG
hydrogel at 25 °C and −20 °C. For the flexible ZIBs with GG/SA hydro-
gel electrolyte, they obtained a capacity of 341.3 and 297.3 mAh g−1
604
Energy Storage Materials 41 (2021) 599–605
Fig. 4. (a) Schematic illustration of the struc-
ture of the solid-state ZIBs. (b) Power-supply
demonstration in normal and bending states.
(c) Discharge curves for normal and bending
states of solid-state ZIBs with GG/SA/EG hy-
drogel electrolytes at 0.3 A g−1 . (d) The ca-
pacity retention of solid-state ZIBs with the
GG/SA/EG hydrogel electrolyte for 1000 bend-
ing cycles test with a bending radius of 10 mm.
after 100 and 1000 bending cycles at 0.3 A g−1 (Fig. S18). This results
in a capacity retention of 98.8% and 86.0% compared to the initial ca-
pacity of 345.5 mAh g−1 . Moreover, the flexible solid-state ZIBs with
GG/SA/EG and GG/SA hydrogel electrolyte were tested using 0 to 1000
bending cycles, and their capacity retention, after 1000 bending cycles,
were 78.3% and 87.2%, respectively (Fig. 5d and Fig. S19).
4. Conclusion
In summary, we obtained a composite hydrogel electrolyte with high
ionic conductivity (25.37 mS cm−1 ) by mixing GG and SA. The ZIBs
with the GG/SA hydrogel electrolyte showed superior electrochemical
performance (354.9 mAh g−1 at 0.15 A g−1 , 137.0 mAh g−1 at 6 A g−1 ,
capacity retention of 91.52% over 1000 cycles) compared to the pure
GG hydrogel electrolyte at room temperature. We also prepared a com-
posite hydrogel with excellent anti-freezing capability. This was done
by introducing EG into GG/SA hydrogel. At −20 °C, the GG/SA/EG hy-
drogel had a high ionic conductivity of 6.19 mS cm−1 , while the corre-
sponding ZIBs had high specific capacity (181.5 mAh g−1 at 0.1 A g−1 )
and good cycling performance (capacity retention of 80.39% over 100
cycles). The ZIBs with the GG/SA and GG/SA/EG hydrogel also showed
excellent flexibility, which showed 87.2% and 78.3% capacity retention
after 1000 bending cycles, respectively. This study opens new possibil-
ities to develop natural polymer-based hydrogel electrolytes with high
ionic conductivity and good anti-freezing capability.
Declaration of Competing Interest
None.
CRediT authorship contribution statement
Jiawei Wang: Conceptualization, Methodology, Investigation, For-
mal analysis, Writing – original draft. Yuan Huang: Methodology, Writ-
ing – review & editing, Supervision. Binbin Liu: Methodology, Investi-
gation. Zixuan Li: Methodology, Investigation. Jiyan Zhang: Method-
ology, Investigation. Guoshen Yang: Validation. Pritesh Hiralal: Val-
J. Wang, Y. Huang, B. Liu et al.
idation. Shunyu Jin: Resources. Hang Zhou: Methodology, Writing –
review & editing, Supervision.
Acknowledgments
This work is supported by Shenzhen Science and Tech-
nology Innovation Committee (No. JCYJ20190806145609284,
GJHZ20190820091203667 and KQTD20190929172522248)
and Guangdong Basic and Applied Basic Research Foundation
(2020A1515010716). Yuan Huang would like to acknowledge support
from the Fundamental Research Funds for the Central Universities,
Sun Yat-sen University. P. Hiralal would like to acknowledge sup-
port from Supported by the Guangdong Introducing Innovative and
Entrepreneurial Teams Program (2019ZT08Z656).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ensm.2021.06.034.
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