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Zwitterionic Sulfobetaine Hydrogel Electrolyte Building

Separated Positive/Negative Ion Migration Channels for
Aqueous Zn-MnO2 Batteries with Superior Rate Capabilities
Funian Mo, Ze Chen, Guojin Liang, Donghong Wang, Yuwei Zhao, Hongfei Li,
Binbin Dong, and Chunyi Zhi*

1. Introduction
Hydrogel electrolytes have attracted increasing attention due to their
potential uses in the fabrication of flexible solid-state batteries. However, The soft and wet hydrogel materials attract
the development of hydrogel electrolytes is still in the initial stage and the increasing attention for the fabrication of
flexible batteries owing to their ability to
number of available strategies is limited. Ideally, the hydrogel electrolyte
perform multiple functions of electrolyte,
should exhibit suitable ionic conductivity rate, mechanical strength, and binder, and separator in aqueous solid-
biocompatibility for safety. In this study, a zwitterionic sulfobetaine/cellulose state batteries.[1,2] Generally, hydrogel
hydrogel electrolyte is fabricated using raw materials from natural plants, electrolytes are composed of polymeric
which exhibits a good biocompatibility with mammalian cells. The intrinsic matrices swollen with tunable water-dis-
zwitterionic groups on sulfobetaine chains can provide separated ion solving electrolyte salts to provide mobile
ions. The traditional hydrogel electrolytes
migration channels for positive and negative ions, which largely facilitates are dominantly based on poly(acrylamide)
electrolyte ion transport. A solid-state Zn-MnO2 battery with a fabricated (PAM), polyacrylic acid, and polyvinyl
zwitterionic gel electrolyte exhibits a very high rate performance. It exhibits a alcohol matrices; sodium polyacrylate;
−1 gelatin, etc.[3–7] Although these hydrogel
specific capacity of 275 mA h g MnO 2
at 1 C. Even up to 30 C, a high capacity
−1
of 74 mA h g MnO is maintained during the charging–discharging for up to electrolytes provide physical frameworks
2
to support the ion transport, they would
10 000 cycles. For wearable applications, the flexible solid-state batteries
not provide considerable improvements in
can be used as reliable and portable sources to power different wearable electrochemical performances. The devel-
electronics such as a commercial smart watch, electroluminescent panel, opment of polymeric hydrogel electrolytes
and color electroluminescence line, which shows their large potentials for is at the primary stage. The number of
use in next-generation flexible and wearable battery technologies. available optional approaches is limited.
Thus, novel hydrogel materials with high
electrochemical performances fabricated
through chemical design are required.
Polyzwitterions are a type of charged polymer bearing unique
F. Mo, Z. Chen, G. Liang, D. Wang, Y. Zhao, Prof. C. Zhi
Department of Materials Science and Engineering zwitterionic groups in a repeat unit, which generally exhibit
City University of Hong Kong high water retention abilities and solubilities.[8,9] The polyzwit-
83 Tat Chee Avenue, Kowloon, Hong Kong SAR 999077, China terions have attracted considerable interest as potential biocom-
E-mail: cy.zhi@cityu.edu.hk patible materials.[10,11] Owing to their high hydration ability and
Dr. H. Li neutral surface charge considering the zwitterionic structure,
Songshan Lake Materials Laboratory
Dongguan, Guangdong 523808, China
sulfobetaine polymers exhibit high resistances to nonspecific
Prof. B. Dong
protein adsorptions.[12] The anionic and cationic counterions on
National Engineering Research Center for Advanced zwitterionic chains can be easily separated under an external
Polymer Processing Technology electric field. The strong electrostatic interactions between the
Zhengzhou University zwitterionic charged groups and electrolyte ions facilitate the
Zhengzhou, Henan 450002, China ion transport.[13–15] In addition, the dipole–dipole physical inter-
Prof. C. Zhi actions between the repeated zwitterionic groups and chemical
Centre for Functional Photonics
City University of Hong Kong double bonds contribute to the formation of a polyzwitteri-
Kowloon, Hong Kong SAR 999077, China onic hydrogel matrix. Moreover, the polar and charged groups
associated with zwitterionic groups can enhance the interfa-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202000035. cial adhesion between the electrodes and gel electrolyte, and
thus the polyzwitterionic hydrogel electrolyte can also be used
DOI: 10.1002/aenm.202000035 as a polymeric binder. Therefore, considering the combined

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advantages, it is of importance to introduce zwitterionic poly-
mers to energy storage applications. However, the “salt-like
structures” of the polyzwitterions usually lead to brittle polym-
erized hydrogels. A reliable approach is desired to enhance the
mechanical properties.
Cellulose nanofibrils, composed of nanofiber assemblies with
diameters of 2 to 20 nm, exhibit unique structural hierarchies and
have been widely used as reinforcing agents.[16,17] Considering the
abundant hydroxyl groups, the hydrophilic skeleton of the cellu-
lose nanofibrils can improve the water containments of hydrogels.
The formed interlaced microporous network can further stabilize
the channels for ion transport.[18] Thus, nanofibrillated cellulose
was used as a mechanically reinforcing additive for the designed
polyzwitterionic hydrogel electrolyte. The traditional lithium-ion
batteries (LIBs) are usually based on hazardous organic electro-
lytes. Thus, their practical applications in wearable electronics
are hindered by safety and biocompatibility issues.[19,20] Recently,
aqueous zinc manganese-dioxide (Zn-MnO2) batteries with
neural/mild electrolytes have emerged as promising alternatives
to LIBs owing to their inherent safety, ecofriendliness, low costs,
and simple fabrications, which are particularly advantageous in
the design of flexible and wearable batteries.[21–23]
In this study, we fabricated a novel hydrogel electrolyte based
on zwitterionic sulfobetaine/cellulose semi-interpenetrating net-
works (ZSC-gel), which provided superior electrochemical perfor-
mances and mechanical strengths in flexible aqueous Zn-MnO2
batteries. The hydrogel electrolyte was synthesized by polymer-
izing the zwitterionic sulfobetaine monomer of [2-(methacryloy-
loxy)ethyl]diethy-(3-sulopropyl) (MAEDS) in a skeleton composed
of cellulose nanofibrils. The zwitterionic structure of the MAEDS
network provided not only a superior polyelectrolyte water reten-
tion owing to the strong electrostatic interactions between zwit-
terionic groups and water molecules, but also ion migration
channels for a large ionic transport, which yielded a higher rate
capability. The cellulose nanofibrils significantly improved the
mechanical properties. Owing to these synergistic effects, the
ZSC-gel electrolyte exhibited an ultrahigh ionic conductivity of
24.6 mS cm−1 and high stretchability of 920%. The Zn-MnO2 bat-
tery with the polyzwitterion hydrogel electrolyte (polyzwitterion-
battery) exhibited a high capacity of 148 mA h g MnO −1
2
at 6.5 C
with a retention of 90.42% of the initial capacity after 1200 cycles.
Even at 30 C, an ultrafast charging–discharging up to 10 000
−1
cycles was achieved with an average capacity of 62 mA h g MnO 2
, and 288.4 eV, assigned to the carbon atoms of saturated hydro-
which further verifies the superior rate capability. Furthermore,
flexible planar and fiber-shaped batteries were fabricated using
the designed ZSC-gel electrolyte, which exhibited excellent flex-
ibilities and/or weavabilities. A tandem unit of three planar bat-
teries in series was fabricated as an energy belt to power various
wearable electronics, while four fiber-shaped devices were inte-
grated into a flexible energy fabric to power two light-emitting
diodes (LEDs) upon bending and stretching deformations, which
shows the large potential for wearable applications.
2. Formulation and Characterization
of the ZSC-Gel Electrolyte
The ZSC-gel consisted of a typical semi-interpenetrating
polymer network, as illustrated in Figure 1a, in which the
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cellulose nanofibrils interact with the covalent networks of
poly[2-(methacryloyloxy)ethyl]diethy-(3-sulopropyl) (PMAEDS)
through physical entanglement and intertwining. All mono-
mers are natural, which implies a good biocompatibility of
the synthetic hydrogel. The synthesis route is illustrated in
Figure 1b and Figure S1, Supporting Information. The polym-
erization of MAEDS monomers was induced by a potassium
persulfate (K2SO4) initiator in an aqueous dispersion con-
taining cellulose nanofibrils with N,N′-methylenebisacrylamide
(MBAA) used as a cross linker. Subsequently, the obtained
hydrogel was immersed into a mixed solution of ZnSO4 and
MnSO4 until complete ion exchange to fabricate the hydrogel
electrolyte. Owing to the abundant carboxyl and hydroxy bonds
on the cellulose chains, the cellulose nanofibrils cross-helically
wind around, form hydrogen bonds with PMAEDS networks
in extended junction zones, and thus significantly improve the
mechanical properties of the gel matrix (Figure S2, Supporting
Information). For comparison, cross-linked/uncross-linked
PMAEDS hydrogels were synthesized by replacing the nano­
fibrillated-cellulose-dispersed solution with deionized water.
The hydrogel structure was investigated by Fourier-transform
infrared (FTIR) spectroscopy and X-ray photoelectron spec-
troscopy (XPS), which revealed the formation of the PMAEDS
matrix with zwitterionic groups. In the attenuated-total-reflec-
tion (ATR) FTIR spectra (Figure S3, Supporting Information),
the characteristic peak at 1038 cm−1 was observed for both pure
MAEDS and synthesized ZSC-gel, indexed to the sulfonate
group of SO3−, which confirms the sulfobetaine structure.
The decreased intensity of the double-bond peak centered at
≈1719 cm−1 demonstrates the opening and connection of the
double bonds of the MAEDS monomer, indicative of a suc-
cessful free-radical polymerization (Figure S3, Supporting Infor-
mation). In addition, the XP survey scan spectrum shows N1s
(400 eV) and S2p (166.5 eV) peaks attributed to two indicative
atoms of MAEDS (ZSC-gel, Figure 2a and Figure S4, Supporting
Information).[24] Typically, the peak in the N1s spectrum corre-
sponds to sulfobetaine ammonium nitrogen (-N+(CH3)2CH2),
while the spectrum of S2p contains two peaks. The first peak,
at 166.5 eV, can be assigned to the sulfobetaine sulfonate anion
(SO3−), while the other peak, at 168 eV, may correspond to
the sulfur in S2O82− originated from the K2S2O8 initiator. The
C1s spectrum exhibits three characteristic peaks, at 284.9, 286.7,
carbons (CC), carbon atom bonding to oxygen (CO),
carbon–sulfur (CS), or carbon–nitrogen (CN), and
carbon atoms in carbonyl groups (CO), respectively.[25]
These results confirm that MAEDS was successfully polymer-
ized to form the ZSC-gel comprising sulfobetaine groups.
The scanning electron microscopy (SEM) image of the ZSC-
gel shows abundant micropores with diameters of 80–150 µm
(Figure 2b) for the migration of electrolyte ions, which pro-
vided a superior ionic conductivity. We compared the mechan-
ical strengths of the pure uncross-linked PMAEDS hydrogel,
cross-linked PMAEDS hydrogel with MBAA, and ZSC-gel
(Figure 2c,d). With the addition of nanofibrillated cellulose, the
ZSC-gel exhibited a high tensile modulus of 24.46 kPa with a
large strain of 920% (Figure S5, Supporting Information), while
the pure cross-linked PMAEDS and uncross-linked PMAEDS
hydrogels exhibited considerably lower tensile moduli of 6.55 and
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Figure 1. Schematic of the fabrication of the ZSC-gel matrix. a) Semi-interpenetrating networks of the ZSC-gel consisting of zwitterionic sulfobetaine
and cellulose nanofibril chains. b) Synthesis of the ZSC-gel. The square frame indicates the migration channel for Zn2+ and SO42− ions.

0.84 kPa, respectively. This demonstrates the substantial
enhancements in mechanical properties by the synergetic con-
tribution of the nanofibrillated cellulose. When the ZSC-gel
was soaked in a ZnSO4–MnSO4 solution, the PMAEDS seg-
ment swelled, but the swelling was remarkably suppressed by
the nanofibrillated cellulose chains (Figure 2c). The photograph
shows that the ZSC-gel was sufficiently robust to endure the in-
depth compression and fully recover after the withdrawal of the
external force, whereas the weak PMAEDS hydrogels were com-
pletely crushed during the compression (Figure 2e). In addition,
the charged groups of the polyzwitterions zone in the molecular
chain of the ZSC-gel exhibited strong electrostatic interactions

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Figure 2. Characterizations of the ZSC-gel. a) XP spectra of the ZSC-gel. b) SEM image of the freeze-dried ZSC-gel. Scale bar: 150 µm. c) Comparison
of the mechanical strengths of the uncross-linked PMAEDS hydrogel, cross-linked PMAEDS hydrogel, and ZSC-gels before and after the soaking in the
ZnSO4–MnSO4 aqueous solution. d) Tensile moduli of the different hydrogels derived from the linear-increase strain ranges in the stress–strain curves.
The inset shows the tensile deformation of the ZSC-gel. e) Optical images of the hydrogels before and after the compression. f) Schematic of the cell
viability experiments on the RAW264.7 cells incubated directly onto the surface of the ZSC-gel. g) Viability of RAW264.7 evaluated by the CCK-8 test.
h) ROS measurement of RAW264.7 cells (2 × 105 cells per well) incubated on the PAM-gel and ZSC-gel films. The control was normal RAW264.7 cells
incubated in 24-well plates. LPS (1 µg mL−1) was used as the positive control. i) Dark-field microscopy images (×400) and SEM images of RAW264.7
cells incubated on the ZSC-gel films.

with the surrounding water molecules, thus providing a
high water retention capacity of the gel matrix (Figure S6,
Supporting Information).
The flexible batteries should be safe for wearable applications
with potentially direct contacts with the human body.[26] The
hydrogel, as a polymer matrix swollen with tunable amounts
of water and dissolved ions, is effective to prevent leakage.
Large-molecular-weight polymers cannot be easily absorbed
by mammalian skin, and thus are often regarded nontoxic.
Some monomers with incomplete reactions in the gel matrix
may be harmful to the human health. However, no extensive
studies have been carried out on the biocompatibilities of

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hydrogels, which are crucial for wearable device applications.
In this study, the biocompatibility of the ZSC-gel was investi-
gated by Cell Counting Kit-8 (CCK-8) and Reactive Oxygen Spe-
cies (ROS) measurements, as described in the experimental
section in Supplementary Information. Murine macrophage
cells (RAW264.7), common pleiotropic cells involved in wound
repair, clearance of apoptotic cells, and tissue remodeling,
were used for direct incubation onto the surfaces of various
hydrogel films (Figure 2f).[27] In the CCK-8 test, the viabilities
of the RAW264.7 cells after the incubations with the ZSC-gel
and poly(acrylamide) hydrogel (PAM-gel) were calculated by
normalization to untreated RAW264.7 cells (Figure 2g). The
viability of the RAW264.7 cells incubated on the PAM-gel was
significantly different from that of the control group, which
implies that the PAM adversely affected the cell incubation.
In contrast, the cell viability of the ZSC-gel was significantly
increased (>98%), which indicates a low cellular cytotoxicity in
the polyzwitterions of the ZSC-gel. In addition, the intracellular
accumulation of ROSs, involved in various chronic diseases
such as diabetes, atherosclerosis, neurodegeneration, cancer,
and aging, was evaluated by using a 2,7-dichlorodihydrofluo-
rescein diacetate (DCFH-DA) fluorescent probe.[28] As shown
in Figure 2h, the DCFH-DA fluorescence intensities of the
vacuity control and positive control lipopolysaccharides (LPSs)
are ≈91 and ≈147 AU, respectively. The intensity of the ZSC-gel
was similar to that of the vacuity control (102 AU), consider-
ably lower than that of the PAM-gel (136 AU), which implies
an insignificant stimulation of the ZSC-gel during the cell
growth. Furthermore, the dark-field microscopy image shows a
larger number of survived RAW264.7 cells incubated with the
ZSC-gel than that for the PAM-gel (Figure 2i). The SEM image
also shows that the RAW264.7 cells incubated with the ZSC-
gel adhered well to the gel-film substrate. A large area with a
large number of visible pseudopodia was observed, whereas the
distinct contraction observed in the comparison cells incubated
with the PAM-gel implies a loss of bioactivity. These results
confirm the biocompatibility of the ZSC-gel, consistent with the
pioneering investigations on zwitterionic polymers.[29,30]
3. Fabrication and Electrochemical Performance
of a Polyzwitterion-Battery
Various pioneering studies have been carried out to analyze the
charge storage mechanisms in aqueous Zn-MnO2 batteries,
from Zn2+ storage to Zn2+/H+ coinsertion and recently reported
high-voltage pure H+ reaction with MnO2.[31,32] α-MnO2, with
its nanorod structure, has been considered a promising cathode
material for a Zn-ion battery. The structure and morphology
of the active material were characterized (Figures S7–S9, Sup-
porting Information). The X-ray diffraction (XRD) pattern of
the hydrothermally synthesized MnO2/carbon nanotube (CNT)
composite, with all characteristic peaks indexed to α-MnO2
(Joint Committee on Powder Diffraction Standards [JCPDS]
44–0141), indicates a crystalline phase (Figure S7a, Supporting
Information).[33,34] Figure S10, Supporting Information, shows
the assembly of a Zn-MnO2 coin cell with the ZSC-gel electro-
lyte for further electrochemical measurements. The thin film
of the ZSC-gel could serve as both electrolyte and separator
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(Figure S11, Supporting Information). The mass of the ZSC-gel
film electrolyte was approximately 0.0723 g, while that of the
liquid electrolyte was calculated to be approximately 0.0506 g.
For comparison, a nonpolyzwitterion pure PAM-gel electro-
lyte was fabricated by replacing the MAEDS with acrylamide
monomer.
Typically, the electrochemical performances of batteries are
determined by their kinetics, which were investigated in this
study by cyclic voltammetry (CV). The CV curves of the polyz-
witterion-batteries are presented in Figure 3a, which show two
cathodic peaks and two anodic peaks. The relationship between
the peak current and scan rate can be expressed by i = avb or
log (i) = blog (v) + log(a), where i is the current, v is the scan
rate, and a and b are adjustable coefficients. Through linear fit-
ting of log(i) and log(v), the b values for cathodic and anodic
peaks 1, 2, and 3 were calculated to be 0.71, 0.65, and 0.62,
respectively, which implies a diffusion-controlled battery and
pseudocapacitance behaviors of the polyzwitterion-battery elec-
trochemistry (Figure 3b).[35] The kinetic behavior of the MnO2/
CNT cathode in the polyzwitterion-battery was further investi-
gated using the discharge galvanostatic intermittent titration
technique (GITT). As shown in Figure 3c, the overvoltage in
region I is only 0.12 V, while the total overvoltage in region II
(0.6 V) is almost five times that in region I, owing to mainly the
large voltage change and slow ion diffusion.[22] The two external
electrolyte ions, H+ and Zn2+, can be transported and inserted
into the MnO2 nanostructure. The diameter of H+ is smaller
than that of Zn2+.[36] Therefore, in the polyzwitterion-battery,
the first discharge plateau originates from the H+ insertion,
while the second voltage plateau originates from mainly the
Zn2+ insertion reaction accompanied by the ongoing insertion
of H+ ions.[22] The electrochemical reaction mechanism was
confirmed by ATR-FTIR spectroscopy and XRD of the MnO2
cathode (Figures S12 and S13, Supporting Information). The
XRD pattern in Figure S13a, Supporting Information, indicates
the formation of MnOOH in the α-MnO2 cathode discharged to
1 V, which is a reaction product of MnO2 crystal with a proton
from water (MnO2 + H+ + e−1 ↔ MnOOH). The sequent OH−
ions gradually react with ZnSO4 and H2O from the aqueous
hydrogel electrolyte and lead to discharge production of zinc
hydroxide sulfate (ZnSO4[Zn(OH)2]3∙xH2O), as shown by the
strong XRD signal in Figure S13b, Supporting Information.[21]
The formation/decomposition of (ZnSO4[Zn(OH)2]3∙xH2O)
was highly reversible. It could revert to pristine α-MnO2 upon
reversal to 1.8 V in the 10th cycle (Figure S13c, Supporting
Information), which shows the stability during the charge–
discharge cycling.
The rate performance of the polyzwitterion-battery was
−1
measured at 1 to 30 C (1 C = 0.308 mA g MnO 2
) in a voltage
range of 0.9 to 1.9 V (Figure 3d). At 1 C, the polyzwitterion-bat-
−1
tery exhibited an average specific capacity of 275 mA h g MnO 2
,
−1
approximately 91% of the theoretical capacity (308 mA h g MnO2 ).
With the increase in current density, values of 232, 181, 154,
−1
134, 121, 104, 87, 80, and 74 mA h g MnO 2
were measured when
the reversible discharge capacity was stabilized at 2, 4, 6, 8,
10, 15, 20, 25, and 30 C, respectively. The average capacity
of the polyzwitterion-battery at 20 C was 31.6.9% of that at
1 C, whereas the Zn-MnO2 battery with the PAM-gel elec-
trolyte exhibited a considerable performance reduction with
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Figure 3. Electrochemical performances of the Zn-MnO2 coin cells with the ZSC-gel electrolyte. a) CV curves in the range of 0.9 to 1.9 V at various
scan rates. b) Linear fit of log(current) versus log(scan rate) of three peaks in the CV curve. c) Discharge GITT curves of the polyzwitterion-battery
(discharged at 50 mA g−1 for 120 s followed by resting for 1 h). d) Cycling performances at different C-rates (1–30 C). e) Discharge–charge curves at
different C-rates in the range of 0.9 to 1.9 V versus Zn2+/Zn. f) Ragone plot (based on the weight of the cathode material) of the polyzwitterion-battery
and other reported aqueous batteries (Zn//β-MnO2,[37] Zn//δ-MnO2,[38] Zn//Zn-VS2,[39] Zn//Zn0.25V2O5,[40] Zn//Na0.95MnO2,[41] Zn//Todorokite,[42]
Al//graphite,[43] Ni//Zn,[44] Ni//Bi,[45] GF//NaTi3O7,[46] LMO//LTO[47]). g) Comparison of the maximum rate performances and cycling performances
of several typical Zn-MnO2 batteries with different electrolytes.[3,4,21,22,34,36,37,48–50] All parameters, including the specific capacity and energy and power
densities, are calculated based on the weight of MnO2 in the cathode.

a large polarization when the C-rate exceeded 10 C (Figure batteries based on ZSC-gel and PAM-gel electrolytes. The
S14, Supporting Information). Notably, the specific capacity polyzwitterion-battery exhibits specific capacities of 148 and
−1 −1
recovered to 268 mA h g MnO 2
with a small voltage hysteresis 105 mA h g MnO 2
at 6.5 C and 16 C with a retention of 90.42%
when the C-rate was returned from 30 to 1 C, that is, approxi- and 84.85% of the initial values after 1200 cycles, respectively.
−1
mately 97% of the initial capacity was preserved. All galvano- At 30 C, a high capacity of 74 mA h g MnO 2
of the polyzwitte-
static charge–discharge (GCD) profiles in Figure 3e exhibit a rion-battery could be retained during the charging–discharging
sloping plateau at 1.4 V owing to the H+ insertion, followed for 10 000 cycles. The ultrafast charging–discharging is attrib-
by a flat plateau at 1.3 V dominantly determined by the Zn2+ uted to the fast ion transfer kinetics of the polyzwitterions. As
insertion, which indicates a stable rate capability. Figure S15, presented in Figure 3f, the polyzwitterion-battery exhibited a
−1
Supporting Information, shows that the capacity could fully high energy density of 386 W h kg MnO 2
at 1 C and could retain
−1
recover sequentially at each stage with the decrease in C-rate a value of approximately 155 W h kg MnO 2
under a power den-
from 30 to 1 C, which confirms the superior reversibility. Con- −1
sity of 6485 W h kg MnO 2
higher than those of the Zn//β-MnO2
sidering the mechanical properties of the film electrolytes, the and Zn//δ-MnO2 counterparts[37,38] and various other aqueous
mass of the as-prepared ZSC-gel film for cyclic performance battery systems.[39–47] The maximum C-rate performances and
measurements was approximately 72.3 mg with a thickness cyclic lifetimes of typical Zn-MnO2 battery systems with dif-
of ≈0.097 mm (Figure S11, Supporting Information). In this ferent electrolytes are summarized in Figure 3g. The polyzwit-
condition, the cycling stability data was obtained with excess terion-battery exhibits superior rate and cycling performances
amount of electrolyte. Figures S16 and S17, Supporting to those of various representative Zn-MnO2 batteries based on
Information, show the cycling performance of the Zn-MnO2 different electrolytes.[3,4,21,22,34,36,37,48–50]

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Figure 4. Operation mechanism of the polyzwitterions of the ZSC-gel electrolyte. a) Schematic of the ZSC-gel electrolyte in a zinc-ion battery under
an external electric field. Under the external electric field, ion migration channels are formed in the gel matrix owing to the electrostatic attractions
between the zwitterionic groups and positive/negative ions. b) AC impedance spectra of the ZSC-gel and PAM-gel electrolytes in the frequency range
of 10 kHz to 0.01 Hz. The inset shows the calculated ionic conductivity. c) Ionic conductivities of the ZSC-gel electrolyte at different bending states
(45°, 90°, 135°, 180°). d) EIS plots of the polyzwitterion-batteries based on the ZSC-gel and PAM-gel electrolytes in the frequency range of 100 kHz to
0.01 Hz. The inset shows the equivalent circuit and fitted EIS data.

4. Mechanistic Analysis of the ZSC-Gel Electrolyte
In terms of molecular structure, the designed ZSC-gel is a type
of polyzwitterionic material bearing both negatively charged
sulfonate group and positively charged quaternary ammonium
group in one repeat monomeric unit of the molecular chain
(zwitterionic characteristic). As illustrated in Figure 4a, under
an external electric field, the ion migration channel can be
formed along the aligned zwitterionic side groups in the gel
matrix, which can largely increase the efficiency of ion trans-
port. Owing to the unique zwitterionic structure of the ZSC-
gel, the dissolved cationic Zn2+ and anionic SO4− ions can
easily overcome the electrostatic attractions by the counterions
and negatively/positively charged groups and can be separated
under the external electric field. Subsequently, the ions easily
transfer along the migration channels to the surfaces of the
electrodes with a reduced energy loss during the ion migra-
tion. Therefore, the rate performance of the solid-state battery
was largely increased (Figure 3d and Figure S14, Supporting
Information).
The ionic conductivities of the ZSC-gel and PAM-gel electro-
lytes were determined by alternating-current (AC) impedance
spectroscopy (Figure 4b). According to the calculations, the ZSC-
gel exhibited a high ionic conductivity of 24.6 × 10−2 S cm−1,
comparable to those of the PAM-gel (17.2 × 10−2 S cm−1) and
other reported zinc-ion-conducting polyelectrolytes.[51–54]
With the increase in content of polyzwitterions, the ionic con-
ductivity increased, and then was almost unchanged for the
ZSC-gels with MAEDS contents above 50%, while the tensile
modulus of the ZSC-gel was decreased at higher MAEDS con-
tents owing to the brittle “salt-like structure” of the polyzwit-
terions (Figure S18, Supporting Information). The ion migra-
tion channels derived from the zwitterionic groups within the
polymer network also facilitated the ionic transport. The ZSC-
gel electrolyte accommodated the repeated interface fluctuation
and enabled a uniform and fast transport of ions throughout
the gel matrix and whole electrode surface. Only small differ-
ences in ionic conductivity of the solid-state Zn//Zn symmetric
cell were observed between the straight and various bending
states (45°, 90°, 135°, 180°), which reveals that the ZSC-gel
electrolyte exhibited electrochemical stability and mechanical
flexibility owing to the contribution by the cellulose nanofi-
brils (Figure 4c). To confirm the efficiency of the ion migration
channel of the ZSC-gel electrolyte, electrochemical impedance
spectroscopy (EIS) was carried out on the Zn-MnO2 full battery
in the range of 100 kHz to 0.01 Hz (Figure 4d). As shown in the
Nyquist plot, the equivalent Faradic charge-transfer resistance
(Rct) of the ZSC-gel electrolyte was calculated to be 124.8 Ω,
considerably smaller than that of the PAM-gel electrolyte of
255.5 Ω. At a high frequency, the interface resistance (Ri) of
the Zn-MnO2 battery with the ZSC-gel electrolyte was lower
than that of the battery based on the PAM-gel electrolyte. This

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Figure 5. Characterizations of the formation of the quasi-SEI layer on the Zn anode owing to the zwitterionic structure of the ZSC-gel electrolyte.
a) Comparison of voltage–time profiles reflecting the cycling zinc stripping/plating performances of Zn//Zn symmetric cells based on various electro-
lytes. b) SEM image and EDS element maps of the anode after 15 electrochemical cycles. Scale bar: 10 µm. c) EIS results for the polyzwitterion-battery
before and after the cycling (up to three cycles). d) XP survey spectrum of the Zn anode after 15 cycles. e) High-resolution XP spectra of C 1s and Zn
2p. f) Schematic of the formation of the quasi-SEI layer between the ZSC-gel electrolyte and Zn anode.

reveals that the zwitterionic gel was more effective to maintain a
more compatible electrode/electrolyte interface than the PAM-
gel electrolyte, which contributed to the higher ion diffusion
coefficient and superior rate performance. To further analyze
the dual ion migration induced by the zwitterionic functional
groups, we calculated the diffusion coefficient of the zinc ions
(DZn) in the ZSC-gel.[55] As shown in Figure S19, Supporting
Information, DZn of the PAM-gel was calculated to be only
0.46 × 10−17 m2 s−1, whereas the ZSC-gel exhibited a consider-
ably higher ion transport capacity (1.18 × 10−17 m2 s−1). This
demonstrates the superior ion transfer kinetics of the ZSC-gel
achieved with the polyzwitterions.
The results suggest that the negatively charged sulfonate
groups along the ZSC-gel electrolyte side chains can exhibit
strong electrostatic interactions with the positively charged
zinc ions, which leads to the formation of a quasi-solid-electro-
lyte-interphase (SEI) layer without dendrites.[56,57] The voltage–
time curve shows that the Zn/ZSC-gel/Zn symmetric cell was
stabilized around 85 mV for over 200 h at 0.5 mA g cm−2,
whereas the other comparison cells based on liquid and
PAM-gel electrolytes exhibited large increases in voltage hys-
teresis, particularly after 120 h (Figure 5a). The charged sul-
fonate groups on the side chains could induce the uniform
deposition of Zn2+ ions onto the anode. The homogeneous
quasi-SEI layer inhibited the localized zinc metal nuclea-
tion and growth, thereby suppressing the Zn dendrite for-
mation. The quasi-SEI layer was confirmed by SEM images
and energy-dispersive spectroscopy (EDS) element maps of

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the zinc anode after 15 electrochemical cycles (Figure 5b
and Figure S20, Supporting Information). In the SEM image
(Figure 5b), the zinc anode after 15 plating/stripping cycles in
the ZSC-gel electrolyte exhibits a smooth surface and dense
and dendrite-free morphology. Based on the EDS results, in
addition to Zn, the quasi-SEI layer was composed of mainly
C, N, and O, which suggests its polyzwitterion structure with
a quaternary ammonium containing Zn2+, which verifies the
existence of a uniform quasi-SEI layer. In contrast, the zinc
anode of the Zn-MnO2 battery with the PAM-gel electrolyte
exhibited abundant sharp Zn dendrites without quasi-SEI
layer after 15 electrochemical cycles (Figure S21, Supporting
Information) owing to the lack of electrostatic interactions
between the PAM-gel and zinc ions.
Furthermore, the quasi-SEI layer could provide homoge-
neous and intimate contacts between the ZSC-gel and elec-
trodes. It also accommodated the interface fluctuation without
breakdown, which provided an even ion transport through the
interface. EIS was carried out to verify this claim. As shown in
Figure 5c, the first semicircle at high frequencies is attributed
to the quasi-SEI layer resistance (Rqs), the medium-frequency
semicircle is related to the charge transfer resistance (Rct), and
the incline at low frequencies corresponds to the Warburg
impedance (Zw), which represents the ion diffusion within the
cathode.[58] As shown in Figure 5c and Figure S22, Supporting
Information, Rqs of the cycled polyzwitterion-battery reaching
equilibrium after three cycles and insignificant change in Rct
reveal an unlimited diffusion in the highly ion conductive
quasi-SEI layer. The small Zw tilt is attributed to the phase
transition of the MnO2 nanocrystal after the first charging.
In contrast, no considerable change in Rqs is observed in the
Nyquist plot of the PAM-gel-based counterpart (Figure S23,
Supporting Information). The XPS performed on the Zn
anode of the polyzwitterion-battery after 15 electrochemical
cycles also indicates that the interface between the gel electro-
lyte and anode was functionalized by the quasi-SEI layer. As
shown in Figure 5d and Figure S24, Supporting Information,
the XP survey spectrum of the Zn anode after 15 cycles shows
N and S element peaks, as expected, which are attributed to
the positively charged quaternary ammonium group and nega-
tively charged sulfonate group of the zwitterions, respectively.
The high-resolution XP spectra of C 1s and Zn 2p show char-
acteristic peaks of CO, CO, CC, and ZnO (Figure 5e),
which confirms the formation of the polyzwitterion-facilitated
quasi-SEI layer, which could facilitate the ion transport and
inhibit the Zn dendrite formation. These results suggest that
the higher performance of the Zn electrochemistry is attrib-
uted to mainly the quasi-SEI layer. As shown in Figure 5f,
zinc ions transfer to the anode surface under the electric field
along the charged sulfonate groups on the side chains of the
ZSC-gel electrolyte. A homogeneous polyzwitterion-facilitated
quasi-SEI layer eventually forms. The quasi-SEI layer pro-
vides an increased number of nucleation sites and adjusts
the charge distribution by the surface modification of sul-
fonate groups, thus inducing the uniform deposition of Zn2+
ions onto the anode and inhibiting the localized zinc dendrite
nucleation and growth. Therefore, the ZSC-gel electrolyte can
significantly increase the cycling performance of the aqueous
Zn-MnO2 battery.
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5. Flexible and Wearable Polyzwitterion-Battery
Generally, the polyelectrolytes could rupture, which would
lead to performance reduction and short circuit upon external
mechanical stimuli in the wearable applications of flexible
batteries. After the toughening with the nanofibrillated cel-
lulose, the mechanical strength of the zwitterionic hydrogel
was substantially higher. Thus, it could resist external stimuli
and maintain the battery performances, which is beneficial to
extend the applications of the polyzwitterion-batteries.
To fabricate a solid-state flexible battery, the ZSC-gel elec-
trolyte, which also served as a separator, was sandwiched
between a MnO2/CNT-coated carbon cloth cathode and flex-
ible Zn anode, as illustrated in Figure 6a. To achieve a higher
flexibility of the battery, electrodeposited Zn onto the soft
carbon cloth was used as a flexible zinc anode (Figure S25,
Supporting Information). The electrodeposited Zn and Zn
foils did not lead to different electrochemical characteristics
of the polyzwitterion-batteries (Figure S26, Supporting Infor-
mation). The resultant planar battery exhibited a capacity of
−1
158 mA h g MnO 2
at 6.5 C with a high retention of 94.9% of
its initial capacity after 500 cycles (Figure S27, Supporting
Information). Regarding the mechanical flexibility, the planar
polyzwitterion-battery with a length L of 7.5 cm and curva-
ture radius R of 1.5 cm was electrochemically stable at var-
ious bending states in the range of 0 to 180° (Figure 6b,c).
A tandem unit of three batteries in series yielded an output
voltage of approximately 5.4 V, which demonstrates the device
scalability (Figure 6d). Considering its robust mechanical
properties, the tandem unit could be used as an energy belt to
power an electronic bracelet watch, electroluminescent panel
(10 cm × 2.5 cm), and color electroluminescence line with a
length of 40 cm (Figure 6e–g), which shows its large potential
for use in wearable electronics.
Using a MnO2/CNT yarn cathode as a fibrous cathode, we
fabricated a prototype fiber-shaped polyzwitterion-battery in a
plastic tube (Figure 6h). The fiber-shaped MnO2/CNT cathode
was fabricated using the simple roll–dip–coating method. The
SEM image (Figure S28, Supporting Information) reveals that
MnO2 nanorods were homogeneously coated on the helix-struc-
tured CNT yarn. The resultant fiber-shaped battery exhibited
maximum volumetric energy density of 7.2 mW h cm−3 and
power density of 2.4 W cm−3 (both of them were calculated
based on the whole battery). The flexible battery also exhibited
superior mechanical and electrochemical stabilities that it could
−1
deliver an average capacity of 130 mA h g MnO 2
at 6.5 C with a
high capacity retention of 77.5% after 300 cycles under twisting
deformation, which shows its good compatibility for wearable
applications (Figure 6i). The reduction in cyclic property of
the fiber-shaped battery compared to that of the planar battery
may be attributed to the complex interdependence of the dis-
crete components in such 1D geometry. The weak component
adhesions among the active materials, 1D current collector, and
electrolyte would also affect its long-term cycling stability. The
specific capacity of the battery was unchanged upon bendings
to different angles in the range of 30 to 180° (Figure 6j). To
demonstrate its wearable application, four fiber-shaped devices
were woven into a cloth, which yielded an “energy” fabric
(Figure 6k). The energy fabric exhibited a tandem voltage up to
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Figure 6. Wearable applications of the polyzwitterion-battery. a) Schematic of the structure of the planar polyzwitterion-battery. b) Flexibility evalua-
tion of the solid-state polyzwitterion-battery. c) Capacitance retentions of the polyzwitterion-batteries at different bending angles. d) GCD curves of
the tandem unit with three flexible batteries in series. Digital photographs of the polyzwitterion-battery tandem unit used to power a e) commercial
smart watch, f) color electroluminescence line, and g) electroluminescent panel. h) Schematic of the fiber-shaped polyzwitterion-battery. i) Cycling
performance of the fiber-shaped polyzwitterion-battery at 6.5 C in a twisting state. j) Capacity retentions of the fiber-shaped battery bent at angles in
the range of 0 to 180°. k) Fabric integrated with four fiber-shaped batteries in series. Two LEDs powered by the energy fabric under l) bending and
m) stretching deformations.

3.5 V to power two LEDs. Its robustness against bending and
stretching deformations makes it compatible with irregular sur-
faces (Figure 6l,m).
6. Conclusions
We synthesized a biocompatible ZSC-gel electrolyte for a
flexible solid-state Zn-MnO2 battery. The zwitterionic structure
of sulfobetaine in the gel matrix provided ion migration chan-
nels facilitating the electrolyte ion transport, which yielded a
high ion conductivity of 24.6 mS cm−1. The cellulose nanofi-
brils stabilized the physical framework of polyzwitterions and
significantly improved the mechanical properties. The biocom-
patibility test showed that the RAW264.7 cells incubated with the
ZSC-gel exhibited a viability larger than 98%, which indicated a
low cellular cytotoxicity in the polyzwitterions of the ZSC-gel.
The as-fabricated Zn-MnO2 battery with the designed hydrogel

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www.advancedsciencenews.com
−1
electrolyte exhibited an energy density of 386 W h kg MnO at
−1
2
1 C and approximately 155 W h kg MnO2 at a power density of
6485 W kg−1 MnO. The polyzwitterion-battery exhibited an
ultrafast charging–discharging even at 30 C, and high capacity
−1
of 74 mA h g MnO 2
. Furthermore, the polyzwitterion-battery
could be subjected to 10 000 cycles at 30 C with an average
−1
capacity of 62 mA h g MnO 2
. To the best of our knowledge, this
is the first report on reversible Zn-MnO2 battery systems with
mild aqueous electrolytes with such high rate capabilities. Flex-
ible planar and fiber-shaped polyzwitterion-batteries were also
fabricated and used as reliable power sources operating under
severe bendings. To demonstrate their wearable applications,
the polyzwitterion-batteries were connected in series as an
energy belt/woven into an energy fabric to power different wear-
able electronics such as a commercial smart watch, LEDs, and
color electroluminescent panel/line. Furthermore, we fabricated
a symmetric supercapacitor with the ZSC-gel, which exhibited
a high electrochemical performance (Figure S29, Supporting
Information). The results demonstrate the versatility of the poly-
zwitterionic electrolyte for use in diverse energy storage devices.
Our zwitterionic gel electrolyte could pave the way for next-gen-
eration flexible and wearable battery technologies.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the National Key R&D Program of China
under Project 2019YFA0705104 and the Government Research Funding
under Project CityU 11305218 and partially sponsored by the Science
Technology and Innovation Committee of Shenzhen Municipality (Grant
No. JCYJ20170818103435068).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
aqueous batteries, hydrogel electrolytes, ion migration channels, rate
capabilities, zwitterionic sulfobetaine
Received: January 5, 2020
Revised: February 19, 2020
Published online:
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