Materials Today Physics 20 (2021) 100458

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Materials Today Physics

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materials-today-physics

Self-healable hydrogel electrolyte for dendrite-free and self-healable

zinc-based aqueous batteries
Wei Ling a, b, c, Funian Mo a, b, c, Jiaqi Wang a, b, c, Qingjiang Liu a, b, c, Yao Liu a, b, c,
Qixin Yang c, Yejun Qiu c, Yan Huang a, b, c, *
a
State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Shenzhen, 518055, China
b
Flexible Printed Electronic Technology Center, Harbin Institute of Technology, Shenzhen, 518055, China
c
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen, 518055, China

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

Article history: The poor stability of zinc anodes caused by uneven deposition/stripping of zinc has inevitably limited the
Received 6 May 2021 practical application of zinc-based aqueous batteries (ZABs). And the self-healing property is very
Received in revised form necessary for improved lifespan and reliability of the flexible batteries under various deformations
6 June 2021
during their daily usage. In this work, a new self-healable hydrogel electrolyte (SHE) with rigid-flexible
Accepted 9 June 2021
Available online 16 June 2021
backbones is synthesized by cross-linking polymerization and composite strengthening. Owing to porous
crosslinking network and more hydrophilic groups, the SHE possesses high ionic conductivity (23.1 mS/
cm at 25
C) and excellent mechanical strength, and the hydrophilic groups are conductive to improve
Keywords:
Zinc-based aqueous batteries
interfacial compatibility between electrode and electrolyte, prompting much more disciplined Zn metal
Self-healable hydrogel plating/stripping. And the dynamic hydrogen bonds derived from the hydroxyl groups of the polymer
Ionic conductivity backbone can prompt self-healing and stretchable property of SHEs. As a result, the assembled flexible
Dendrite-free growth zinc-manganese dioxide batteries delivered a high capacity of 304 mAh g1 at 0.5 A g1 and good cycling
Self-healable batteries stability with a capacity retention of 83.1% (vs. 62.5% with polyacrylamide) after 1500 charge/discharge
cycles at 5.0 A g1. Furthermore, the flexible batteries with SHEs can recover electrochemical perfor-
mance with over 95% healing efficiency after 5 cycles of complete breaking/healing.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction aqueous batteries (ZABs) have been recognized as one of the

With high energy density and good cycling stability, lithium ion
batteries (LIBs) have governed the rechargeable battery market
among consumer electronics, portable electronics and power bat-
teries in the last few decades, but insufficient lithium resources,
flammable organic electrolytes, and safety issues still limit further
large-scale application of LIBs [1e3]. By contrast, aqueous batteries
possess high safety, environmental friendliness, low assembly cost
and high rate performance, benefiting from the usage of aqueous
electrolyte (safe reliability and high ionic conductivity) and no
demand of water-free and oxygen-free conditions [4e8]. Owing to
the advantages of metallic zinc anodes (low electrochemical
potential, 0.76 V vs. standard hydrogen electrode and high spe-
cific capacity, 820 mAh g1 and 5855 mAh cm3), zinc-based
* Corresponding author. State Key Laboratory of Advanced Welding and Joining,
Harbin Institute of Technology, Shenzhen, 518055, China.
E-mail address: yanhuanglib@hit.edu.cn (Y. Huang).
most attractive candidates for next-generation high energy density
storage systems compared with other aqueous batteries [9e11].
Nevertheless, the uncontrollable zinc dendrite growth in liquid
electrolyte (LE), would pierce the separator and induce short-
circuiting, thus cause inferior cycling stability issues for current
ZABs [12e14]. So far, great efforts have been devoted to suppress
zinc dendrite growth for ZABs, such as zinc metal surface modifi-
cation [15], 3D conductive nanostructure [16,17], nanolayer coating
[18,19], concentrated electrolytes [20,21] and hydrogel electrolytes
[22,23].
By turning to the hydrogel electrolytes from current LEs, the
issue of zinc dendrite growth may be relieved to some extent,
contributing to an improved cycling stability for ZABs [24]. In
addition, the hydrogel electrolytes provide high flexibility and
reliable electrochemical properties for portable and flexible elec-
tronics compared with LEs [25e27]. Especially, when the hydrogel
electrolytes have self-healing property, the flexible batteries can
stand against local stress under various deformations during their

https://doi.org/10.1016/j.mtphys.2021.100458
2542-5293/© 2021 Elsevier Ltd. All rights reserved.
W. Ling, F. Mo, J. Wang et al.
daily usage, which can greatly prolong the lifespan and reliability of
the electronic system [28e30]. Recently, some self-healing hydro-
gel electrolytes have been reported to be applied in the aqueous
batteries, such as polyvinyl alcohol (PVA) [31,32], sodium poly-
acrylate (PANa) [33] and sodium polyacrylate-sodium alginate
(PANa-Ca-SA) [34], which have been achieved great progress in the
self-healing property of batteries. The self-healing mechanisms can
be generalized to two categories of reversible covalent bond
(cycloaddition reaction, disulfide bond, acylhydrazide bond and
boron-oxygen bond etc.) [29,35] and dynamic non-covalent bond
(hydrogen bond, ionic bond, metal ligand interaction, p-p stacking
and host-guest identification etc) [36e38]. However, many self-
healing polyelectrolytes displayed poor salt solubility and insuffi-
cient water absorbing capacity, especially in the mild environment,
which vastly restrict electrochemical performance of batteries (low
ionic conductivity) and leave harmful effect (acid or alkali condi-
tions) on environment and human body [39e41]. Therefore, it is of
great significance to design a kind of self-healing polyelectrolytes
with excellent electrochemical performance in the mild condition
for ZABs.
Herein, we design a self-healable hydrogel electrolytes (SHE)
with excellent stretchability and high ion conductivity to regularize
the metallic zinc electrochemical behavior for flexible and mild
ZABs. The SHEs are synthesized by cross-linking polymerization of
agarose molecular chain and polyacrylamide (PAM), and the car-
boxymethyl cellulose (CMC) was introduced into the composite
electrolytes to strengthen their film-forming property. The greater
porous crosslinking network of SHE ensures the high ionic con-
ductivity (23.1 mS/cm at 25
C) and uniform deposition of Zn metal.
The symmetric zinc-metal batteries with SHEs can maintain a
smaller voltage hysteresis (~80 mV) and be stably charged/dis-
charged for up to 300 h at 5 mA/cm2 while the batteries with LEs
generated a short circuit after only less than 40 h operation, and
pure PAMs showed an ever-increasing voltage hysteresis (from
100 mV to 200 mV) during 270 h operation. Assembled with Zn/
carbon cloth anode and a-MnO2 cathode, the flexible zinc-
manganese dioxide batteries delivered a high capacity of 304
mAh g1 at a current density of 0.5 A g1 and good cycling stability
with a capacity retention of 83.1% (120 mAh g1) after 1500 charge/
discharge cycles at 5.0 A g1. Furthermore, due to the hydrogen
bonding derived from abundant hydroxyl groups in the poly-
electrolyte networks, the a-MnO2//Zn batteries with the SHE can
repair their electrochemical performance with over 95% healing
efficiency after 5 cycles of thorough breaking/healing.
2. Results and discussions
2.1. Design of the self-healable hydrogel electrolyte for dendrite-free
and self-healable zinc-based aqueous batteries
The schematic diagram of SHE with self-healing process is
shown in Fig. 1a, which was fabricated by a free radical polymeri-
zation of acrylamide monomers among the polymer networks of
agarose molecular and CMC chains. As described in the experi-
mental section, the agarose powder was dissolved in the deionized
water at high temperature (90
C), and then acrylamide, initiator
and cross-linking agent were added under cooling state. Finally, the
precursor solution was gelatinized at 70
C for 24 h after dissolving
CMC, ZnSO4 and MnSO4 (Fig. S1). The agarose is a kind of natural
plant gums that usually are used as thickening agent and coagulant,
such as biological medium. Benefiting from rich hydroxyl groups,
the agarose is expected to play a vital role in the self-healing
property of SHE membrane via hydrogen-bond interaction
(Fig. 1b) [43,44]. As a common film-forming agent, the CMC was
applied to further strengthen the mechanical capacity of SHE
2
Materials Today Physics 20 (2021) 100458
(Fig. S2). Compared with other metal anodes, Zn anode is able to
remain a reversible deposition/stripping in aqueous electrolytes,
which prompt ZABs relatively high voltage platform and capacity.
Unfortunately, like conventional lithium-ion batteries, the dendrite
growth phenomenon is also liable to occur in zinc metal anode by
the influence of uneven electric field and large current polarization,
and the phenomenon with on-going may puncture the separator
and result in an internal shorting failure of ZABs. As a schematic
diagram displayed in Fig. 1c, the zinc foil is easily subjected to
dendrite growth in the LE due to uneven electric field distribution,
and the pure PAM also not fully resolve the issue of zinc dendrite
growth because of poor film mechanical properties and unstable
electrode/electrolyte interface. By contrast, owing to porous
crosslinking network and more hydrophilic groups, the SHE pos-
sesses high ionic conductivity and excellent mechanical strength,
and the hydrophilic groups are conductive to improve interfacial
compatibility between electrode and electrolyte, which can effec-
tivity solve dendrite growth problem through lowering the over-
potential of metal nucleation/deposition, and the risk of the
electrolyte punctured from dendrites.
2.2. Characterization of the self-healable hydrogel electrolyte
The scanning electron microscopy (SEM) image reveals that the
SHE exhibits a more highly porous 3D morphology compared with
PAM (Fig. 2aef), and this structure could facilitate a higher water
uptake and offer rapid ion transport pathways. In addition, it is
shown that the three-dimensional cross-linking networks exist in
the porous structure of SHE (Fig. 2e and f), which may be capable of
improving the mechanical strength and stretchability of gel elec-
trolyte. Fourier-transform infrared spectroscopy (FTIR) was applied
to analyze the functional groups and bands of SHE solid electrolyte.
The spectra of PAM and SHE show that there are several absorption
bands at 3350 cm1, 2941 cm1, 1650 cm1 and 1411 cm1 [42],
which are attributed to NeH stretching vibration, CeH stretching
vibration, C]O stretching vibration and symmetric eCOO
stretching vibration, respectively (Fig. 2g). Besides, compared with
PAM, the SHE possesses a stronger absorption bands at 1114 cm1
corresponding to hydroxyl functional groups (CeOH stretch) [45].
The abundant hydroxyl groups of the polymer backbone are
conductive to the formation of hydrogen bonds in the SHE and
improve the hydrophilicity of gel electrolyte. The dynamic
hydrogen bonds can prompt self-healing and stretchable property
of SHEs (Fig. S3), and the high hydrophilicity is helpful for
enhancing ionic conductivity and interfacial compatibility of SHE
solid electrolyte. To verify this point, the ionic conductivities of the
PAM and SHE membranes were calculated from the AC impedance
spectra via the assembly of symmetrical stainless-steel//stainless-
steel batteries (Fig. 2h). According to the equation (s ¼ d/SR), the
SHE with adding 1.0g agarose (PAM/CMCþ1.0g agarose) possesses
the highest the ionic conductivity of 23.1 mS/cm at room temper-
ature compared with other electrolytes (Fig. S4), which is two times
higher than that of the pure PAM (11.6 mS/cm). The impedance
measurement of stainless-steel/SHE/stainless-steel batteries at
variable temperatures is displayed in Fig. S5a, and the activation
energy (Ea) of SHE electrolytes could be calculated as z0.024 eV
based on the Arrhenius-type behavior between logs and 1/T
(Fig. S5b), indicating a lower ion transport barrier. Besides, the SHE
was able to still stain a high ionic conductivity close to that of
original condition during different healing cycle, suggesting a su-
perior self-healing property (Fig. S6). Furthermore, the linear
sweep voltammetry (LSV) was used to determine the electro-
chemical stability window of various electrolytes through asym-
metric Zn//stainless-steel batteries. As shown in Fig. 2i, the SHE
shows a broader electrochemical stability window than that of LE
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 1. a) Composition of SHEs and its self-healing illustration. b) The origin of self-healability (hydrogen bond). c) Schematic illustrations of morphology evolution for Zn foils with
LEs (i), pure PAMs (ii) and SHEs (iii) during Zn stripping/plating cycling.

and PAM, especially in the positive direction. The stable voltage batteries still show a short circuit after 285 h at 5 mA cm2 (Fig. S9),
window of SHE is ascribed that the hydrogel and more hydrogen suggesting the sole CMC is not able to contribute to the dendrite-
bond interactions can strengthen the binding force of free water free and self-healing property of hydrogel electrolyte. Further-
molecule and thus decrease reaction activity of aqueous electrolyte. more, the short circuit phenomenon more likely occurred in the
symmetric Zn/LE/Zn batteries after 90 h, 47 h and 37 h at 1.0, 3.0
and 5.0 mA cm2, respectively (Fig. S10a-c). In addition, compared
2.3. Zn metal deposition/stripping behavior based on the self-
with PAM, the symmetric Zn/SHE/Zn batteries could keep a lower
healable hydrogel electrolyte
and stable internal resistance during 100 cycles (Fig. 3k), which is
caused by the high ionic conductivity and good interfacial
To study the influence of various electrolytes on the zinc
compatibility of SHE solid electrolyte. With the increases of cycles,
dendrite growth, the symmetric Zn//Zn batteries were assembled
the internal resistance of symmetric Zn/LE/Zn batteries was instead
to test their long cycle stability (Fig. 3). Comparing the surface
reduced (Fig. S11a), which may be attributed to the fact that the
morphology of zinc metal anodes after deposition/stripping at a
more severe dendrite growth in the LE can shorten ion distance in a
current density of 1.0, 3.0 and 5.0 mA cm2, the SHE can prompt a
way until short circuit. To study the reversible Zn deposition/
smoother and dendrite-free Zn anode after 200 cycles in contrast to
stripping behaviors, the Zn//Ti batteries were assembled to perform
that of PAM (Fig. 3aef), and the Zn anode in LE possesses an obvious
the cyclic voltammetry (CV) at 0.5 mV s1 for various electrolytes.
protuberant surface morphology after only 50 cycles (Fig. S7),
As shown in Fig. 3l, the SHE possesses a lower electrochemical
suggesting that SHE is able to homogenize the deposition/stripping
polarization of Zn deposition/stripping than that of PAM in the
of zinc ion on the zinc metal surface. As shown in the chro-
wide range of 0.5 to 3.0 V. Besides, the oxygen evolution potential
nopotentiometry curves, the symmetric Zn/SHE/Zn batteries
of LE is lower than 2.5 V, and once again indicate that gel electro-
exhibit a more stable and lower hysteresis of below 50 mV for 700 h
lytes (SHE and PAM) possess more stable voltage window than LE
than that of PAM (90 mV after 420 h) at current density of
(Fig. S11b). In a word, the highly reversible Zn anode is mainly
1.0 mA cm2 (Fig. 3g and Fig. S8a). Especially, with the current
attributed to the porous crosslinking network and more hydro-
density increases to 3 and 5 mA cm2, the symmetric Zn/SHE/Zn
philic groups of SHE, and thus the SHE possesses high ionic con-
batteries maintain more stable voltage hysteresis of below 100 mV
ductivity and excellent mechanical strength. Furthermore, the
for 500 h and 300 h. By contrast, the symmetric Zn/PAM/Zn bat-
hydrophilic groups on the hydrogel electrolyte interface are
teries show a higher hysteresis of above 100 mV for 400 h at
conductive to improve interfacial compatibility between electrode
3 mA cm2, and possess ever-increasing voltage hysteresis up to
and electrolyte, which can effectively solve dendrite growth prob-
204 mV and subsequent short circuit after 266 h at 5 mA cm2
lem through lowering the overpotential of metal nucleation/
(Fig. 3hej and Fig. S8b). Similarly, the symmetric Zn//PAM/CMC//Zn
3
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 2. SEM image of (aec) PAM and (def) SHE at different magnifications. g) FTIR spectra of PAM and SHE. h) AC impedance spectra of the PAM and SHE in the frequency range from
10 kHz to 0.01 Hz and ionic conductivities calculated from the spectra. i) Linear sweep voltammetry (LSV) plot of the LE, PAM and SHE at a scan rate of 1.0 mV s1.

deposition. redox activity of MnO2 in SHE, multi-sweep cyclic voltammetry

(CV) is performed under different scan rates ranging from
0.1 mV s1 to 1.0 mV s1 (Fig. 4a). The shape and peak current of CV
2.4. Electrochemical performances of the flexible MnO2/SHE/Zn
curves maintain a good coherence and linear relation with the
batteries
increasing scan rate, suggesting a minor polarization toward the
stable electrochemical reaction. And the two pairs of redox peaks
Based on the above excellent results of SHEs for high Zn2þ
appear on the CV curves under various scan rates, which belong to
conduction and dendrite-free growth, the full battery tests were
the extraction/insertion of Hþ (Peak 2 and Peak 4) and Zn2þ (Peak 1
performed on the assembled flexible zinc-based batteries. In
and Peak 3) into a-MnO2 host, respectively [47]. Besides, the CV
addition, manganese dioxide (MnO2), including a-MnO2, b-MnO2,
curves have been almost unchanged during 30 cycles of scanning,
g-MnO2, d-MnO2 and l-MnO2, is a widely applied cathode material
which also prove a more reversible electrochemical cycling process
in ZABs, which has both relatively high specific capacity and
for flexible MnO2eZn batteries based on the SHE (Fig. 4b). And the
discharge voltage plateau compared with other electrode materials,
EIS result of flexible MnO2eZn batteries was displayed in Fig. 4c,
such as V-based cathodes, Prussian blue analogs (PBAs) and organic
indicating a smaller internal resistance of the full cell caused by the
materials [46]. Thus, the MnO2/carbon cloth has been selected as
excellent ionic conductivity and interfacial compatibility of SHE
cathode and matched with Zn metal anode. To prepare the flexible
membrane. As a result, the prepared MnO2/SHE/Zn batteries
batteries, the MnO2 cathode was blade-coated onto carbon cloth,
delivered a reversible capacity of 304 mAh g1 close to theoretical
and the flexible anode was fabricated by depositing zinc metal on
capacity (308 mA g1) at 0.5 A g1, and still kept a discharge ca-
the carbon cloth. And the flexible MnO2/SHE/Zn batteries were
pacity of 130 mAh g1 at high current density of 5.0 A g1 (Fig. 4d
assembled to characterize the electrochemical performance (Fig. 4).
and e), which manifest an excellent rate capability surpassing most
In this work, the MnO2 active material is confirmed as a-phase from
of reported works [48]. And GCD of MnO2/SHE/Zn batteries retain a
XRD patterns (JCPDS: No.00-44-0141) (Fig. S12a). To further boost
favorable stability with returning to 0.5 A g1 after cycles of rate
the electric conductivity of active material, the multiwalled carbon
performance (Fig. 4f). Furthermore, the MnO2/SHE/Zn batteries
nanotube (CNT) was introduced into the cathode to form a three-
were able to preserve an approving capacity retention of 83.1% (110
dimensional conductive network (Fig. S12b-d). To research the
4
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 3. SEM images of the Zn metal anodes with a-c) PAM and d-f) SHE after zinc stripping/plating for 200 cycles under the current density of 1 mA cm2, 3 mA cm2 and 5 mA cm2
with areal capacity of 1.0 mAh cm2. The scale bars are 2 mm. g-h) Cycling performance of Zn/SHEs/Zn symmetric cells at 1 mA cm2 and 3 mA cm2, and i) the comparison of
chronopotentiometry profiles of Zn//Zn symmetric cells based on PAM and SHE at 5 mA cm2. Inset: The Zn plating/stripping voltage profile at different cycles. j) Galvanostatic
discharge-charge curves (GCD) of Zn//Zn symmetric cells at 3 mA cm2. k) EIS results for the Zn//Zn symmetric cells based on PAM and SHE before and after 100 cycles. l) CV curves
of Zn deposition/dissolution in Zn//Ti foil cells at the scan rate of 0.5 mV s1 between 0.5 and 3.0 V.

mAh g1) at large rate of 5.0 A g1 after 1500 cycles, greatly out-
stripping the cycling stability of LE (33.9% capacity retention, 45.5
mAh g1) and PAM (62.5% capacity retention, 80.9 mAh g1)
(Fig. 4g). According to the comparison of the electrochemical per-
formance of the MnO2//Zn batteries based on SHEs with previous
works in the Table S1, the a-MnO2//Zn batteries based on SHEs
display a high rate-capability and ultralong lifespan, surpassing
that of most reported works. The highlighted rate capability and
cycling stability of MnO2/SHE/Zn batteries is mainly derived from
the above analytical factors: (1) The SHE can be conductive to a
smoother and dendrite-free Zn anode during long term deposition/
stripping, and the more hydrogen bond interactions can reinforce
the binding force of free water molecule and thus enhance the
electrochemical stability of aqueous electrolyte. (2) The highly
porous 3D morphology and cross-linking networks prompt a high
ionic conductivity of SHE, and the abundant hydrophilic groups of
SHE skeleton can effectively improve the interfacial compatibility
between solid state electrolyte and electrode materials, which

5
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 4. a) Multi-sweep cyclic voltammetry (CV) of flexible Zn/SHE/MnO2 batteries at different scan rates from 0.1 to 1 mV s1. b) CVs of flexible Zn/SHE/MnO2 batteries at 1 mV s1
during different cycles. c) EIS results for flexible Zn/SHE/MnO2 batteries. d) GCD at various current densities ranging from 0.5 to 10.0 A/g. e) Rate capability of flexible Zn/SHE/MnO2
batteries at various rates. f) GCD at initial seven cycles at 0.5 A/g. g) Long-term cycling performance at a high current density of 5.0 A/g.

contributes to benign zinc ion transport across the electrolyte and
its interface to ensure an outstanding rate capability of MnO2/SHE/
Zn batteries. In addition, the flexible Zn/SHE/MnO2 batteries after
long-term cycling still possessed a minor internal resistance vari-
ation compared with the original state (Fig. S13). All of these ad-
vantages result in a durable cycling stability of MnO2/SHE/Zn
batteries. For better revealing the stable performances of electrode
material in the MnO2/SHE/Zn batteries, the XRD patterns of MnO2
cathode and Zn metal anode at charged state were examined before
and after 1500 cycles at 5.0 A/g (Fig. S14). The electrode materials
both show a good structural stability without obvious irreversible
phase transition. Moreover, the behavior of zinc ions insertion/
extraction into a-MnO2 can be determined from the XPS results
(Fig. S15). As shown in the XPS fitting peaks of Zn 2p, Mn 2p and O
1s, the binding energies of electronic orbits in the a-MnO2 under-
went a reversible variation for zinc ions insertion/extraction during
1500 cycles, demonstrating a stable and reversible electrochemical
behavior of a-MnO2 cathodes in the MnO2/SHE/Zn batteries for
long-term cycling.
2.5. Self-healing property and external force resistance of the
flexible MnO2/SHE/Zn batteries
The self-healing property can protect the flexible batteries to
stand against local stress under various deformations during their
daily usage, which can greatly prolong the lifespan and reliability of
the electronic system. As an actual presentation, the flexible MnO2/
SHE/Zn batteries could normally power a clock (Fig. 5a), and the
clock shut up right away when the flexible batteries was cut in half
(Fig. 5b) and immediately back to work after splicing the two parts
(Fig. 5c), which confirms that the flexible MnO2/SHE/Zn batteries
possess a good self-healing property. Besides, the electrochemical
performance of flexible MnO2/SHE/Zn batteries were measured
before and after multiple cutting/self-healing cycles. Fig. 5d shows
EIS data of flexible batteries possess a low internal resistance and
change slightly during five times of cutting/self-healing. Similarly,
CV of flexible MnO2/SHE/Zn batteries exhibit a nice repeatability for
5 cutting/self-healing cycles, suggesting the self-healing process
didn't significantly affect the electrochemical polarization for redox

6
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 5. a-c) Photographs of the self-healing flexible battery powering a clock before cutting (left), after cutting (middle), and after self-healing (right). d) EIS data and e) CV of the
flexible Zn/SHE/MnO2 batteries before and after multiple cutting/self-healing cycles. f) GCD profiles before and after multiple cutting/self-healing cycles at 3.0 A/g, and g) corre-
sponding healing efficiency performance. h) Rate capability comparison of Zn/SHE/MnO2 batteries with pristine and the firth cutting/self-healing state, and i) GCD of Zn/SHE/MnO2
batteries after the firth cutting/self-healing at various current densities ranging from 0.5 to 10.0 A/g.

reaction (Fig. 5e). Moreover, during 5 cutting/self-healing cycles,
the flexible MnO2/SHE/Zn batteries still maintained a uniform GCD
curves at current density of 3.0 A/g and possessed a high healing
efficiency of above 95% (Fig. 5f and g). To show the influence of self-
healing processes on the rate capability of flexible batteries, the rate
performance of Zn/SHE/MnO2 batteries after the firth cutting/self-
healing was compared with that of the pristine one (Fig. 5h).
Although the capacities of Zn/SHE/MnO2 batteries at the firth
cutting/self-healing state have been reduced, the flexible batteries
still possessed distinct charge/discharge plateaus at 0.5 A/g and
retained no low capacities at large current densities range from 1.0
A/g to 10 A/g (Fig. 5i). Furthermore, the Zn/SHE/MnO2 batteries
after the firth cutting/self-healing exhibited a capacity retention of
80% (101 mAh/g) at 5.0 A/g after 800 cycles, indicating a decent
cycle performance for the self-healing flexible batteries (Fig. S16).
The excellent electrochemical performance of flexible batteries
after the cutting/self-healing is mainly attributed to the good self-
healing ability of SHE, which is displayed in Fig. S3.
Besides self-healing property, the electrochemical performance
of flexible Zn/SHE/MnO2 batteries with other extreme conditions
7
was evaluated in Fig. 6. It is observed that the whole discharge
curves of flexible batteries via six hammerings possessed a minor
fluctuation compared with initial one at current density of 3.0 A/g
(Fig. 6a). Moreover, the capacity retention of flexible batteries
maintained 88.5% after 12 times hammer strikes (Fig. 6b, Fig. S17a),
and the each striking intensity kept approximately 20 N23~ N which
is calculated by equation (F (N) ¼ 9.8 (N/kg)  m (kg)) from the
platform scale (Fig. S17b-c), indicating an excellent mechanical
property of SHE solid state electrolyte. In addition, fixed at various
bending states of 30
, 60
, 90
and 180
, the flexible batteries
retained a subtle variation of GCD curves and high capacity reten-
tion at 3.0 A/g (Fig. 6c). After 10 washing times for over 15 min per,
the flexible Zn/SHE/MnO2 batteries can keep a capacity retention of
85.9%, and still power the electronic watch underwater, illustrating
a highlighted waterproof mechanical capacity and adhesion force of
SHE (Fig. 6d). To further confirm mechanical property of the flexible
batteries, the 22 holes were drilled across the flexible Zn/SHE/MnO2
batteries and formed a typeface of HIT. And the flexible batteries
still power an electronic watch without short circuit phenomenon
(Fig. 6e). Moreover, the electronic watch could be powered by the
W. Ling, F. Mo, J. Wang et al. Materials Today Physics 20 (2021) 100458

Fig. 6. Electrochemical performance of flexible Zn/SHE/MnO2-batteries in various destructive experiments. a) Impact resistance and b) capacity retention of flexible Zn/SHE/MnO2-
batteries after different hammering tests at 3.0 A/g. c) Illustration of bending flexible Zn/SHE/MnO2-batteries at different angles and the corresponding GCD curves at 3.0 A/g.
Capacity retention of flexible Zn/SHE/MnO2-batteries after d) soaking tests, e) punching tests. f) Cutting test of flexible Zn/SHE/MnO2-batteries.

flexible MnO2/SHE/Zn batteries after tailoring several times, and it
prove a favorable mechanical property of SHE membrane again
(Fig. 6f).
3. Conclusion
In summary, we successfully designed a self-healable hydrogel
electrolyte for dendrite-free and self-healable zinc-based aqueous
batteries. The hydrogel electrolyte was synthesized by cross-linking
polymerization of agarose molecular chain and PAM, and the CMC
was introduced into the composite electrolytes to strengthen their
film-forming property. Benefiting from the highly porous 3D
morphology and cross-linking networks, the SHE exhibits a high
ionic conductivity of 23.1 mS/cm at 25
C, and the abundant hy-
drophilic groups of SHE skeleton can effectively improve the
interfacial compatibility between solid state electrolyte and elec-
trode material, contributing to a smoother and dendrite-free Zn
8
anode in the symmetric batteries during long term deposition/
stripping up to 300 h at current density of 5.0 mA/cm2. Assembled
with Zn/carbon cloth anode and a-MnO2 cathode, the flexible Zn/
SHE/MnO2 batteries delivered a high capacity of 304 mAh g1 at a
current density of 0.5 A g1 and long cycling stability with a ca-
pacity retention of 83.1% (110 mAh g1) after 1500 charge/discharge
cycles at 5.0 A g1. Due to the hydrogen bonding derived from
abundant hydroxyl groups in the polyelectrolyte networks, the SHE
possesses a superior self-healing property and mechanical capacity
compared with reported works (Table S1), which makes a-MnO2//
Zn batteries exhibit a high healing efficiency of over 95% after 5
cycles of complete breaking/healing. In addition, the flexible Zn/
SHE/MnO2 batteries can also power an electronic device and stand
against extremely harsh conditions, such as hammering, bending,
washing, drilling and tailoring, suggesting a practical value for
flexible energy storage in the future. It is reasonable to believe that
this work can be expected to boost the progress of high-
W. Ling, F. Mo, J. Wang et al.
performance ZABs and other wearable energy storage devices.
4. Experimental section
4.1. Synthesis of self-healable hydrogel electrolytes (SHE)
The SHE was prepared via a free radical polymerization under
thermal curing the precursor mixture [42]. First, 1.0 g commercial
agarose powder (AR grade, Alfa) was absolutely dissolved into
40 mL deionized water under extensive stirring at 95
C for 30 min.
Under cooling to 80
C, the 1 mol L1 ZnSO4 (AR grade, Aladdin) and
0.1 mol L1 MnSO4 (AR grade, Aladdin) were added into above
solution for a stirring process of 15 min, and then 30 mg potassium
persulfate (AR grade, Aladdin) and 10 mg N,N0 -methyl-
enebisacrylamide (AR grade, Sigma) were sequentially added to the
mixture solution. After that, 3 g acryl amide (AR grade, Aladdin) and
0.5 g carboxymethyl cellulose (AR grade, Aladdin) was dissolved
and stirred at 50
C for 1 h, and the as-fabricated precursor solution
was injected into a polypropylene (PP) mold and polymerized at
70
C for 24 h to obtain SHE. For comparison, polyacrylamide (PAM)
was fabricated as similar process as that of SHE without adding
agarose and carboxymethyl cellulose. And the liquid electrolyte
(LE) was prepared through added 1 mol L1 ZnSO4 and 0.1 mol L1
MnSO4 into the 20 mL deionized water, and followed by half-hour
stirring for standby application.
4.2. Synthesis of MnO2@CNT cathode
MnO2@CNT was fabricated via a modified co-precipitation and
followed by hydrothermal method. First, the commercial carbon
nanotubes (CNT) with a diameter of 10~30 nm and a length of
5~10 mm (Shanghai Macklin Biochemical Co., Ltd) were refluxed in
nitric acid (AR, Aladdin) at 80
C for 6 h, and then adequately
washed with deionized water for several times. After that, 0.05g as-
purified CNT was re-dispersed in 50 mL deionized water via mag-
netic stirring for 1 h. Then, 0.98 g Mn(CH3COO)2$4H2O (AR grade,
Shanghai Macklin Biochemical Co., Ltd) was dissolved in the
dispersed solution under mixing thoroughly for 30 min. Where-
after, 27 mL aqueous solution containing 0.42 g KMnO4 (AR,
Aladdin) was slowly added drop-wise into above solution and
stirring for 30 min. After ultrasonic dispersion for 10 min, the mixed
solution was transferred to a 100 mL Teflon-lined autoclave and
heated at 120
C for 12 h. After cooling, the obtained MnO2@CNT
was collected by vacuum filtration accompanied by continuous
washing with deionized water, and finally dried in a vacuum oven
at 80
C for overnight.
To fabricate the flexible cathode, MnO2@CNT active materials,
Super P, and polyvinylidene fluoride (PVDF) binder was mixed in
NMP (N-methyl-2 pyrrolidone) with a mass ratio of 8:1:1, and then
the cathode slurry was casted on the carbon cloth and dried at a
vacuum oven at 80
C for 12 h. And as-prepared flexible cathode
contains approximately the active load of 1e2 mg cm2.
4.3. Preparation of flexible Zn anode
In order to match the flexible MnO2/SHE/Zn batteries, the Zn
metal was electrodeposited on the carbon cloth substrate for flex-
ible Zn anode, which used carbon cloth and zinc plate (pu-
rity > 99.99%, Sigma) as working electrode and counter electrode in
an aqueous electrolyte of 1 mol L1 ZnSO4 (AR grade, Aladdin) and
1 mol L1 KCl (AR grade, Aladdin). And electroplating process was
performed at 0.8 V vs Zn foil for 30 min employing an electro-
chemical workstation (CHI 760D).
9
Materials Today Physics 20 (2021) 100458
4.4. Characterization methods
The morphology of gel electrolytes and Zn anodes were
measured via SEM (SU8020) operated at 10 kV and TEM (JEM-
2100F) operated at 200 kV. The composition of gel electrolytes
skeleton was analyzed from Fourier transform infrared spectra
(Vertex 80, Bruker) with the frequency range from 400 to
4000 cm1. The structure and phase of electrodes were determined
by XRD (D/max 2500). And the XPS spectra of MnO2@CNT cathode
with different cycles was tested by applying a Thermo Scientific
ESCA Lab 250Xi instrument with 200 W Al Ka radiation and a base
pressure of 3  1010 mbar in the analysis chamber.
4.5. Electrochemical measurements
The ionic conductivities of the gel electrolytes were tested by AC
impedance spectroscopy instrument from electrochemical work-
station (CHI 760D) with the frequency range between 0.01 and
106 Hz. The gel electrolytes were sandwiched between two
stainless-steel electrodes (SS) and the Zn2þ ionic conductivities (s)
can be calculated as following equation (1):
s ¼ d=Rs (1)
Where d represents the distance between two SS (cm), S is the area
of the gel electrolytes (cm2), and R is the ohmic resistance (U).
The activation energy Ea was calculated, according to the
following Arrhenius law (2):
s ¼ A exp ðEa=RT Þ (2)
where A is the frequency factor, Ea is the activation energy, R is the
molar gas constant and T is the absolute temperature. The elec-
trochemical window of electrolytes can be determined from the
linear sweep voltammetry (LSV) using SS/electrolytes/Zn at a scan
rate of 1 mV s1. Cyclic voltammetry (CV) curves of the flexible
MnO2/SHE/Zn batteries were measured based on a two-electrode
system where MnO2 and Zn were used as working electrode and
counter electrode, respectively. The galvanostatic discharge-charge
(GCD) tests were conducted with a battery test system (Land
CT2001A). The symmetric liquid ZIBs were assembled by CR2032-
type coin cells consisting of LEs, zinc electrodes and glass fiber
film served as separate membrane. The symmetric solid-state ZIBs
were assembled by the zinc electrodes and gel electrolyte in the
form of sandwich structure. And the electrochemical performance
of flexible MnO2/SHE/Zn batteries with planar thin film shape were
performed in the voltage range of 1.0 Ve1.85 V.
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.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (No. 21805063), the Natural Science Founda-
tion of Guangdong Province for Distinguished Young Scholars (No.
2018B030306022), the Project of International Science and Tech-
nology Cooperation in Guangdong Province (No.
2020A0505100016), the Shenzhen Sauvage Nobel Laureate Labo-
ratory for Smart Materials, and Research Innovation Fund of Harbin
Institute of Technology (No. HIT.NSRIF.2020063).
W. Ling, F. Mo, J. Wang et al.
Credit author statement
Y.H. and W.L. managed the project and guided the research; Y.H.
and W.L. designed the experiment. W.L. carried out the material
synthesis, characterizations and electrochemical measurements
with the helps from F.M., J.W., Q.L., Y.L., Q.Y. and Y.Q. W.L. involved
in the discussion. W.L. wrote the manuscript with the supervision
of Y.H. and all authors have approved the final manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.mtphys.2021.100458.
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