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Redirected Zn Electrodeposition by an Anti-Corrosion

Elastic Constraint for Highly Reversible Zn Anodes
Ruirui Zhao, Ying Yang, Ganxiong Liu, Renjie Zhu, Jingbo Huang, Zhiyuan Chen,
Zhonghui Gao, Xiao Chen, and Long Qie*

stands out for its high theoretical capacity

With advantages such as high theoretical capacity, low cost, and nontoxicity,
Zn metal has been widely investigated as an anode for aqueous batteries.
However, the problems of dendrite formation and sustained corrosion
originating from severe interfacial side reactions and uncontrolled Zn elec-
trodeposition in aqueous electrolytes significantly slows down the practical
application of Zn metal anodes. To address these issues, herein, an anti-cor-
rosion elastic constraint (AEC) is introduced that is built with nanosized TiO2
and polyvinylidene fluoride (PVDF) matrix to Zn anode, where the PVDF layer
serves as an elastic H2O/O2-blocking layer and the decorated TiO2 nanopar-
ticles assist uniform Zn electrodeposition. With this corrosion-inhibition and
electrodeposition-redirection coating, the electrodeposition consistency and
thermodynamic stability of the Zn anode are significantly improved, enabling
a long-term stable plating/stripping performance for 2000 h with an ultralow
overpotential (<50 mV) and a high average Coulombic efficiency (>99.4%)
for 1000 cycles without obvious dendrite formation. Even at a high current
density of 8.85 mA cm−2 with limited Zn supply (DODZn = 60%), stable Zn
deposition is achieved over 250 h. When coupled with a MnO2 cathode, the
AEC-Zn anode shows a remarkably enhanced full-cell cycling stability, indica-
tive of high reliability of aqueous Zn batteries for practical application.
1. Introduction
Recent explosions of electric vehicles and grid energy storage
have raised great concerns for the safety of rechargeable bat-
teries, which Professor John Goodenough always emphasizes.[1]
For the traditional rechargeable batteries, the safety issue is
mainly ascribed to the use of the flammable liquid organic
electrolyte. In this context, the development of energy-storage
systems employing intrinsically nonflammable aqueous elec-
trolytes is imperative. For the aqueous batteries, the Zn anode
R. Zhao, Dr. Y. Yang, R. Zhu, J. Huang, Z. Chen, Dr. Z. Gao,
X. Chen, Prof. L. Qie
Institute of New Energy for Vehicles
School of Materials Science and Engineering
Tongji University
Shanghai 201804, China
E-mail: qie@tongji.edu.cn
G. Liu
School of Automotive Studies
Tongji University
Shanghai 201804, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202001867.
DOI: 10.1002/adfm.202001867
(820 mAh g−1 or 5855 mAh cm−3) and
low negative potential (−0.762 V vs the
standard hydrogen electrode (SHE)).[2]
Although Zn anodes have been widely
used in commercial primary batteries
(such as Zn||MnO2 batteries),[3] their
applications in rechargeable aqueous bat-
teries remain a challenge due to low Cou-
lombic efficiency (CE) during repeated Zn
plating/stripping processes.[4]
Fundamentally, the loss of Zn metal
during the electrochemical processes is
mainly due to 1) the sustained chemical
corrosion due to serious interfacial reac-
tions with water or dissolved O2; and
2) the uncontrolled Zn dendrite formation
caused by nonuniform Zn electrochemical
exfoliation/deposition, which additionally
promotes the chemical corrosion. Because
of poor thermodynamic stability of Zn in
aqueous electrolytes, the chemical corro-
sion of Zn is responsible largely for the
low reversibility of Zn anode. According
to the Pourbaix diagram, the interfacial
reactions between the electrolyte and Zn metal inevitably occur
in aqueous electrolyte,[5] especially at the presence of dissolved
O2, which lead to the formation of loose by-products (mainly
zinc hydroxides and zincates) on the surface of Zn.[6] Unlike
the successful lithium-ion systems, where the solid electrolyte
interphase (SEI) film formed on graphite anode could serve as
a dense protective layer to prevent further side reactions with
the electrolyte, the loose by-products on the surface of Zn fail
to prevent the inner Zn metal from being exposed to the elec-
trolyte and thus aggravate the corrosion of Zn.[6b] On the other
side, during the Zn plating process in aqueous electrolyte, Zn
has a strong tendency to electrodeposit as hexagonal flakes,
which are known as Zn dendrites.[7] Such loose electrodepos-
ited Zn could not be thoroughly exfoliated during the following
stripping process, leading to the formation of residual inactive
Zn and hence a significant decrease in CE. Furthermore, due
to the low Zn/Zn2+ potential (−0.762 V vs SHE), the H2 evolu-
tion is unavoidable during the zinc deposition process, causing
increase in the pH value of the electrolyte and the by-products
accumulation.[8]
To actualize the rechargeability of aqueous Zn-metal bat-
teries, we need to adequately address both the sustained chem-
ical corrosion and uncontrolled dendrite-formation problems
for Zn anodes. Up to now, many strategies have been proposed

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to improve the reversibility of Zn anodes, such as designing
new electrolytes with reduced water activity,[9] accommodating
Zn into 3D hosts, and so on.[10] For example, Wang et al.
employed a highly concentrated electrolyte with significantly
reduced water activity, and obtained a dendrite-free Zn plating/
stripping at nearly 100% CE.[11] Using 3D metal–organic frame-
work or MXene as Zn hosts, dendrite-free Zn electrodeposition
was also observed with improved plating/stripping kinetics.[12]
Most recently, Archer co-workers reported the use of graphene
as an epitaxial substrate to direct the electrodeposition behav-
iors of Zn, and demonstrated excellent reversibility over thou-
sands of cycles.[7]
Despite the great progress achieved on Zn reversibility, it
should be noted that the scale-up possibility and the cost issues,
which are critical for practical applications, have been rarely
considered. In this context, the construction of an artificial pro-
tective layer onto the surface of Zn is more practical.[13] It was
reported that coating a porous CaCO3 layer onto Zn could guide
the uniform and bottom-up Zn electrodeposition and thus sta-
bilize the plating/stripping of Zn.[14] However, only the electro-
chemical performance at a low current density (0.25 mA cm−2)
with limited capacity (0.05 mAh cm−2) was reported, which
might be due to the fragile nature of CaCO3. So far, achieving
highly reversible and long-life Zn anodes, especially under high
current densities (>10.0 mA cm−2), via a low-cost and high-scal-
ability method still remains a big challenge.
Inspired by successful design of the artificial SEI film for
lithium metal,[15] herein, we introduce an anti-corrosion elastic
constraint (AEC) as an artificial protective layer to stabilize
the Zn anodes. AEC is constructed with TiO2 nanoparticles-
decorated polyvinylidene fluoride (PVDF) matrix where PVDF
with excellent mechanical flexibility serves an elastic constraint
to relieve the interfacial reactions, and nanosized TiO2 particles
redirect the even electrodeposition by modulating the current
distribution. With this corrosion-inhibition and electrodeposi-
tion-redirection protection, the electrodeposition consistency
and thermodynamic stability of Zn anodes are significantly
improved, enabling a long-term stable plating/stripping per-
formance for 2000 h with an ultralow overpotential (<50 mV)
and a high average CE (>99.4%) for 1000 cycles without
obvious dendrite formation. Even at a high current density
of 8.85 mAh cm−2 with limited Zn supply (DODZn = 60%), a
stable Zn deposition is observed for over 250 h. When coupled
with a MnO2 cathode, the AEC-Zn anode shows an excellent
full-cell cycling stability, indicative of the reliability for the prac-
tical development of aqueous Zn batteries. The as-proposed
method provides not only a low-cost and effective strategy to
stabilize the Zn anodes, but also a fundamental understanding
toward Zn electrodeposition.
2. Results and Discussion
To prepare the AEC layer, TiO2 powder with a particle size
of ≈100 nm (Figure S1, Supporting Information) was first
dispersed into a solution of PVDF dissolved in 1-methyl-
2-pyrrolidone (NMP), and then the solution was drop cast onto
the surface of Zn plates followed by slow evaporation of NMP
at 40 °C. Compared with the most reported methods for Zn
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protection, such a drop-casting approach is highly scalable and
low-cost.
As seen from the scanning electron microscopy (SEM)
images in Figure 1a–c, after the drop-casting procedure, the
TiO2 nanoparticles are anchored tightly into the PVDF matrix,
forming a dense AEC layer with a thickness of ≈5 µm, which is
much thinner than that of the reported protective coatings for
Zn metals (e.g., 40 µm).[16] In addition, the use of high amount
of glutinous PVDF (30 wt%) also guarantees the flexibility and
elasticity of the AEC coating,[17] which is essential for accommo-
dating the volumetric change during the Zn plating/stripping
processes. The elasticity of the AEC layer was evaluated on a
nanoindentation machine. Based on the elastic modulus col-
lected from 12 points (Table S1, Supporting Information), the
calculated average elastic modulus of AEC is 2.67 GPa, which is
slightly lower than that of the pure PVDF film (3.50 GPa), but
still higher than those of the most reported protective coatings
for Li metal.[18] It has been reported that an elastic modulus
higher than 1 GPa is enough to suppress the growth of Li den-
drites.[19] Here, the elasticity of the AEC layer is expected to be
strong enough to accommodate the volumetric change of Zn
electrodeposition.[20]
To examine the anti-corrosion properties of the AEC coating,
we soaked the Zn plates without and with AEC coating into
an aqueous electrolyte (2 m ZnSO4 solution). As shown in the
photos of Figure 1d, the metallic Zn plate turned gray after
4 days with white powder covering on its surface, indicative of
the formation of the chemical-corrosion products due to the
undesirable interfacial side reactions between the unprotected
Zn and ZnSO4 solution. In contrast, the AEC-protected Zn
plate remained lustrous after 7 days, revealing the significant
improved thermodynamic stability of AEC-Zn against to the
aqueous electrolyte (Figure 1e; Figure S2, Supporting Informa-
tion). The surfaces of the Zn plates before and after soaking
tests were further checked with an optical microscope equipped
with a 3D height scanner. As shown in Figure 1h,k, the AEC-
protected Zn plate soaked in ZnSO4 solution for 7 days shows
clear machining marks with similar height fluctuation to that
of fresh Zn plate (Figure 1f,i). In contrast, the electrolyte-soaked
bare Zn plate shows a rough surface with a maximum height
difference of 33.0 µm (Figure 1g,j), which is much higher than
that of electrolyte-soaked AEC-Zn, demonstrating that the AEC
layer effectively protects the Zn plate from chemical corrosion
in the aqueous electrolyte. The superb anti-corrosion capability
of AEC-Zn also proves that the AEC layer has successfully pre-
vented the direct contact of Zn metal with water or dissolved O2
and mitigated the interfacial side reactions.
The AEC coating can not only suppress the chemical cor-
rosion of Zn, but also redirect the Zn electrodeposition and
reduce the electrochemical corrosion of Zn. To reveal the role
of AEC coating on the Zn electrodeposition behaviors, we
assembled symmetrical cells in beakers with Zn or AEC-Zn
plates (Figure 2a,d) for electrochemical plating/stripping of Zn.
The cells were tested at a current density of 0.667 mA cm−2 for
100 cycles. After the plating/stripping tests, the cycled bare Zn
plates were broken at the position of the electrolyte-air interface
(Figure S3a, Supporting Information), confirming the involve-
ment of oxygen in the corrosion process. The cycled Zn plate
is covered by thick mossy products (Figure 2b; Figure S3a,
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Figure 1. The characterizations of bare Zn and AEC-Zn plates and the comparison of their anti-corrosion performance in the aqueous electrolyte
(2 m ZnSO4 solution): top-view SEM images of a) bare Zn and b) AEC-Zn plates; cross-sectional SEM images of c) the AEC-Zn plate with the inset
showing the thickness of the AEC coating; the optical photos for the d) bare Zn and e) AEC-Zn before and after being soaked for 4 days and 7 days; the
high-magnification optical and corresponding 3D height images for the surfaces of f,i) fresh Zn plates, g,j) electrolyte-soaked Zn plates, and h,k) elec-
trolyte-soaked AEC-Zn plates; the wavy lines in (f–h) show the corresponding height profiles for the orange line segments. Here, the AEC coating on
AEC-Zn was peeled off from AEC-Zn plates for the morphology characterizations.

Supporting Information), while the AEC-Zn plate remains
dense and clear after being tested under the same condition
(Figure 2e; Figure S3b, Supporting Information). The 3D height
images clearly show that the cycled AEC-Zn plate (Figure 2f)
has a smaller height fluctuation than that of cycled Zn plate
(Figure 2c), indicating that the AEC layer effectively protects the
Zn from corrosion even after the long-term plating/stripping
test.
To further study the effect of the AEC layer on the mor-
phology of the cycled Zn anodes, SEM test was carried out
(Figure 2g–j; Figure S4, Supporting Information). Bare Zn
plate exhibits a rough and porous surface stacked loosely by
hexagonal flakes after the plating/stripping test, which agrees
with the previously reported results.[21] Not only the surface,
as marked in the blue regions in Figure 2h, pits with a depth
up to 25 µm were also observed in the bulk of the Zn plate,
confirming the poor thermodynamic stability and uncon-
trolled Zn electrodeposition in aqueous electrolytes. In con-
trast, with the AEC coating, Zn2+ ions tend to electrodeposit in
the form of monolithic and compact morphology (Figure 2i–j;
Figure S4, Supporting Information), and negligible corrosion
or dendrite was found on the surface of AEC-Zn after the same
plating/stripping test. The sharp morphology contrast between
the cycled Zn and AEC-Zn plates proves that the AEC layer
is efficient in redirecting the electrodeposition, inhibiting the
dendrite formation and alleviating the volumetric change of Zn
during the long-term electrochemical processes.
The mossy products on the surface of the cycled Zn plates
were checked with X-ray diffraction (XRD) and energy-
dispersive X-ray spectroscopy (EDS). In Figure 2k, strong XRD
peaks belonging to hydrated Zn compounds such as Zn4(SO4)
(OH)6·4H2O, ZnSO3·2.5H2O, and Zn4(SO4)(OH)6·5H2O
are observed in the bare Zn plates after 100 plating/stripping
cycles. The formation of a large amount of Zn-containing by-
products explains the loss of Zn during the electrochemical
process. Unlike Li-ion batteries, where the (electro-)chemical
reactions between the graphite anodes and the ethylene car-
bonate (EC)-based electrolytes can result in a stable and robust
solid electrolyte interface on the surface of graphite and hence
prevent the further side effects. For Zn anodes in aqueous elec-
trolytes, the loose products formed on the Zn surface further
expose the inner fresh Zn metal to the corrosive electrolytes,
and thus accelerate the side reactions and deteriorate the elec-
trochemical performance. The corrosion degrees of the soaked

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Figure 2. The comparison of the electrochemical stability of Zn and AEC-Zn plates: the setup of the symmetrical a) Zn||Zn and d) AEC-Zn||AEC-Zn cells
in beakers; the optical and corresponding 3D height images for the surfaces of b,c) cycled Zn plate and e,f) cycled AEC-Zn plate; the SEM images for
g,h) cycled Zn plates (g: top view, h: cross-sectional view) and i,j) cycled AEC-Zn plates (i: top view, j: cross-sectional view); and k) the XRD patterns of
the cycled Zn and AEC-Zn plates. Here, the symmetrical cells were assembled in beakers and charged/discharged at a current density of 0.667 mA cm−2
for 100 cycles; the AEC layers on the cycled AEC-Zn plates in (b, e, and i) were peeled off while the one in (j) was kept for the characterizations of
AEC-Zn plates.

Zn plates were further quantified based on the XRD results.
Here, we define the corrosion degree as the ratio of the inten-
sity of the strongest peak of the main by-product (peak (004)
of Zn4(SO4)(OH)6·4H2O at 2θ = 17.1°) to that of Zn (peak (101)
at 2θ = 43.2°). The calculated corrosion degree of the soaked
AEC-Zn is 0.189, only about one-fifth of that of bare Zn plates
(0.926), confirming that the AEC coating has adequately pro-
tected the Zn metal during the electrochemical process, which
is also verified by the EDS results in Figure S5, Supporting
Information.
The long-term stability and reversibility of Zn anodes are crit-
ical factors for their practical applications. To examine the sta-
bility of the Zn electrodes, we first tested polarization curves of
Zn||Zn and AEC-Zn||AEC-Zn cells at a scan rate of 0.05 mV s−1.
As shown in Figure S6, Supporting Information, the AEC-
Zn||AEC-Zn cell has an extraordinary steady polarization curve,
revealing the superb stability of the AEC-Zn electrodes. The
galvanostatic plating/stripping performance of symmetrical
Zn||Zn and AEC-Zn||AEC-Zn cells was tested at a current den-
sity of 0.885 mA cm−2. Figure 3a displays the plating/stripping
voltages. The AEC-Zn||AEC-Zn cell shows stable voltage profiles
for 2000 h with the voltage hysteresis gradually decreasing from
50 to 27 mV, having much higher stability as compared with
the most reported Zn anodes (Figure S7, Supporting Informa-
tion). While the Zn||Zn cell exhibits frequent voltage fluctua-
tion, and internal short-circuit signals (sudden voltage drops)
are observed after only around 300 h. It is also noticed that the
dead Zn||Zn cell is dehisced while the AEC-Zn||AEC-Zn cell
remains unchanged even after 2000 h (inset of Figure 3a), indi-
cating that gas formation (H2 evolution) is suppressed in the
AEC-Zn||AEC-Zn cell during the long-term Zn plating/strip-
ping process. Besides, the AEC-Zn||AEC-Zn cell delivers more
stable plating/stripping voltages than the Zn||Zn cell at high
current densities (Figure S8, Supporting Information). The dif-
ferences in cycling stability are also confirmed by the electro-
chemical impedance spectroscopy (EIS) (Figure 3b; Figure S9,
Supporting Information). Unlike the cells with protective coat-
ings, the intrinsic resistances and the charge transfer resist-
ances of the symmetrical cell using bare Zn electrodes gradu-
ally increased with cycling, implying the increased internal
resistance due to the formation of side-reaction products on the
surface. Furthermore, even at an ultrahigh current density of

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Figure 3. The Zn plating/stripping performance for bare Zn plate and AEC-Zn plate: a) long-term cycling performance in symmetrical cells with a cur-
rent density of 0.885 mA cm−2 with the inset showing the photos of the cycled cells; the Nyquist plots b) of the symmetrical Zn||Zn and AEC-Zn||AEC-Zn
cells after different cycles; c) cycling performance of the symmetrical cells with limited Zn supply at a current density of 8.85 mA cm−2 and an areal
capacity of 8.85 mAh cm−2; the inset of (c) shows the photos of the cycled electrodes.

20 mA cm−2 (Figure S10, Supporting Information), the AEC-
Zn||AEC-Zn cell could enable cycling for 250 h, much longer
than that of the Zn||Zn cell (<30 h).
For rechargeable aqueous Zn batteries, excess Zn is
usually used to compensate for the Zn loss during the elec-
trochemical cycling, which greatly counteracts the energy
density advantage of Zn batteries. Considering this, we
further checked the plating/stripping performance of bare
Zn and AEC-Zn under a limited-Zn condition. The tests
were carried out by using symmetrical cells at a high cur-
rent density of 8.85 mA cm−2 and a high areal capacity of
8.85 mAh cm−2, corresponding to 60% of the total areal
capacity of the Zn foil used (thickness: 25 µm, areal capacity:
14.6 mAh cm−2) (Figure 3c). Due to the accelerated accu-
mulation of the side-reaction products and the loss of the
active Zn under the high plating/stripping current density,
the control Zn||Zn cell shows a sudden rise in voltage polari-
zation only after around 10 h. While the AEC-Zn||AEC-Zn
cell exhibits steady charge/discharge response with a low
polarization of ≈70 mV over 250 h under the same draconian
deep-discharge condition, confirming that the AEC coating
is highly effective in redirecting Zn electrodeposition and
reducing Zn loss. To find out the reason for the short life
of the deeply charged/discharged Zn||Zn cell, we disassem-
bled the cycled Zn||Zn and AEC-Zn||AEC-Zn cells. From the
photo­graphic images of the cycled Zn electrodes in the inset
of Figure 3c, we can see that the cycled bare Zn plate is com-
pletely corroded and breaks into small pieces, whereas the
cycled AEC-Zn remains intact without apparent Zn rupture
or thickness change (Figure S11, Supporting Information).
To evaluate the effect of the AEC coating on the revers-
ibility of Zn, CE measurement was carried out with Zn||Ti
and Zn||AEC-Ti cells in 2 m ZnSO4 electrolytes. The test was
performed by plating 0.885 mAh cm−2 of Zn onto the Ti or
AEC-Ti substrate, and then stripping to 0.2 V. The ratio of the
amount of the stripped Zn to that of the plated Zn in each cycle
determines the CE. As displayed in Figure 4a, the Zn||AEC-Ti
cell exhibits a very stable CE over 1000 h at a current density
of 1.77 mA cm−2, and the average CE is as high as 99.4% after
the initial three activation cycles. In contrast, the Zn||Ti cell fails
after less than 400 cycles and shows fluctuating CE especially
after 300 cycles, implying the unstable Zn plating/stripping on
bare Ti substrate. The contrast in reversibility and cyclability
of the Zn anodes could also be confirmed by their polarization
voltages during cycling. In Figure 4b, the polarization voltage of
Zn||Ti cell increased from 50.0 mV at the 150th cycle to 70.4 mV
after 350 cycles, while the polarization voltages of Zn||AEC-
Ti cell decreased gradually from 71.2 mV at the 150th cycle to
55.1 mV at the 1000th cycle, indicating an extraordinary steady
plating/stripping. The AEC-Zn shows ultrahigh CE and cycla-
bility as compared with other reports in Figure 4c.
To further understand the effect of the AEC coating on the
Zn-electrodeposition behaviors, an optical microscope was used
to in situ monitor the surface morphology evolution of the zinc
electrodes (bare Zn and AEC-Zn) during the Zn plating pro-
cess. For the observation, homemade optical cells were con-
structed with transparent glass plates and a current density of
10 mA cm−2 was applied to the cells. Figure 5a and Video S1,
Supporting Information, show the photographic images. Zn
protrusions started to form randomly on the surface of the bare

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Figure 4. The CE tests of Zn||Ti and Zn||AEC-Ti cells: a) CE of Zn plating/stripping at a current density of 1.77 mA cm−2 with an ending charging voltage
of 0.2 V, b) the charge/discharge curves for Zn||Ti and Zn||AEC-Ti cells at different cycles, and c) the comparison of the CE of AEC-Zn with those of
the reported Zn anodes.
Zn after 10 min of plating, and proliferated to tree-like Zn den-
drites with the proceeding of the electrochemical plating. Such
dendrites may bridge the electrodes and result in short circuits
(Figure S12, Supporting Information), which is dangerous for
battery application. Due to the brittle nature of the Zn den-
drites, the growth of the dendrites was accompanied by the for-
mation of ruptured Zn or as-called “dead Zn.” Such host-free
Zn could hardly be reused in the following stripping process,
which is responsible for the low CE of the bare Zn electrode.
In contrast to the electrodeposition behaviors of bare Zn, with
the elastic constraint of the AEC layer (marked in the blue
region in Figure 5b), the Zn tends to electrodeposit under the
AEC layer and propels evenly, so no protrusion or dendrite is
observed on the surface of AEC-Zn plate even after 30 min of
plating (Video S2, Supporting Information). The uniform Zn
electrodeposition indicates that the AEC layer redirects the Zn
nucleation and growth processes.
To understand the importance of TiO2 nanoparticles in AEC
on the cycling stability of the Zn electrodes, we compare the
plating/stripping behaviors of samples with PVDF coating and
AEC coating in both symmetrical Zn||Ti cells. For comparison,
the thickness of the PVDF coating was also controlled to ≈5 µm
(Figure S13a, Supporting Information). After 100 cycles, the
PVDF-Zn plate exhibits a sheet-like surface with many cracks
(Figure S13b, Supporting Information), similar to the cycled
bare Zn (Figure 2g), implying that the TiO2 nanoparticles in
the AEC are critical in redirecting the Zn electrodeposition. In
addition, as marked in the cross-sectional SEM images of the
cycled PVDF-Zn plate (Figure S13c,d, Supporting Information),
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uneven and loose products are observed under the PVDF layer,
apparently different from the cycled AEC-Zn (Figure 2i,j). In
Figure S14, Supporting Information, with PVDF coating, the
symmetrical cell shows improved cycling stability compared
to Zn||Zn cell but fails after about 800 h, which is less than
one-half of that of the AEC-Zn||AEC-Zn cell. Besides, the CE
of the Zn||PVDF-Ti cell also shows a shorter cycling life than
that of Zn||AEC-Ti (Figure S15, Supporting Information). Fur-
thermore, to verify the uniqueness of TiO2, we prepared ZnO-
PVDF-coated Zn electrodes and Al2O3-PVDF-coated Zn elec-
trodes by using the same method as AEC-Zn. As shown in
Figure S16, Supporting Information, no obvious improvement
in cycling stability was observed for the symmetrical cells with
these coated Zn electrodes as compared to the bare one. All of
the above results clearly substantiate the importance of TiO2
nanoparticles in AEC.
Based on the results discussed above, we illustrate the
schemes for the Zn plating/stripping behaviors of bare Zn,
PVDF-Zn, and AEC-Zn (Figure 5c, Supporting Information).
For bare Zn, the poor Zn plating/stripping performance is
mainly due to the serious interfacial reactions with water or
dissolved O2 (chemical corrosion, pit I) and the uncontrolled
Zn deposition and exfoliation (electrochemical corrosion,
pit II). With the introduction of the AEC coating, both the
chemical and electrochemical corrosion of Zn could be effec-
tively suppressed: 1) the AEC layer not only serves as a dense
H2O/O2 blocking layer to avoid the direct contact but also as
an elastic constraint to accommodate the volumetric change
during the Zn plating/stripping processes; 2) the decorated
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Figure 5. The zinc-electrodeposition behaviors of a) bare Zn plate and b) AEC-Zn plate using an in situ optical microscope at a current density of
10 mA cm−2, and c) the illustrations of Zn plating/stripping behaviors for bare Zn plate, PVDF-Zn, and AEC-Zn plate in aqueous electrolytes (2 m ZnSO4).
Here, pit I represents the pits produced by the chemical corrosion of Zn, while pit II stands for the Zn loss caused by the uneven exfoliation.

TiO2 nanoparticles in AEC act as a Zn-electrodeposition redi-
rector by providing favorable nucleation sites and regulating
the local currents during the electrochemical plating/stripping
processes, and thus guarantees the uniform and dense Zn
electrodeposition.
The advantages of the AEC-Zn anode were also further veri-
fied in full cells using MnO2 cathodes (Figure 6). MnO2 was
prepared via a hydrothermal method and its purity was checked
by XRD characterization (Figure S17, Supporting Information).
Here, MnSO4 (0.1 m) was added to the electrolyte (2.0 m ZnSO4)
to suppress the disproportionation reaction of MnO2. The
cyclic voltammetry (CV) curves in Figure 6a show that both the
Zn||MnO2 and AEC-Zn||MnO2 cells present two pairs of cath-
olic/anodic peaks, corresponding to the two-step reverse oxida-
tion/reaction between MnO2 and MnOOH.[22] It is noticed that
the AEC-Zn||MnO2 cell shows higher reduction voltages but
lower oxidation voltages than those of Zn||MnO2 cell, indicative
of improved reaction kinetics for the AEC-Zn||MnO2 cell.
The long-term cycling stability of the full cells was tested at
2 C (C = 308 mA g−1) between 1.8 and 1.0 V. Figure 6b com-
pares the charge/discharge voltage profiles for Zn||MnO2 and
AEC-Zn||MnO2 cells at the second cycle. The AEC-Zn||MnO2
cell presents similar charge/discharge curves to Zn||MnO2 cell
but reduced voltage hysteresis between the charge/discharge
curves, consistent well with the CV results. Figure 6c presents
the cycling performance of the full cells. Although Zn||MnO2
cell delivers a higher initial charge capacity (256 mAh g−1) than
that of AEC-Zn||MnO2 cell (244 mAh g−1), the capacity fades to
103 mAh g−1 after 300 cycles. The fast decay in electrochemical
performance is mainly due to the continuous corrosion of the
unprotected Zn anode. With AEC-Zn as the anode, the cycling
stability is significantly enhanced with a higher capacity reten-
tion (234 mAh g−1) after 300 cycles (Figure 6c).
3. Conclusion
We have demonstrated stable and high-efficiency Zn plating/
stripping by introducing an AEC coating onto the surface of Zn
anodes for aqueous Zn batteries. The H2O/O2 insulating AEC
layer can not only isolate the Zn metal from corrosive aqueous
electrolytes but also guide the uniform and dendrite-free elec-
trodeposition for Zn. The electrodeposition-redirection and
corrosion-inhibition protection provide Zn anodes remarkably
improved electrodeposition consistency and thermodynamic
stability. A long-term stable plating/stripping performance for
over 2000 h is attained with an ultralow overpotential (<50 mV)
and a high average CE (>99.4%) for 1000 cycles without obvious
dendrite formation. More importantly, the AEC-Zn exhibits
steady charge/discharge responses even under a draconian
deep-discharge condition (60% DODZn) with a limited Zn
supply (DODZn = 60%) and a high plating/stripping current
density of 8.85 mA cm−2. By coupling the AEC-Zn anode with
MnO2 cathode, we have achieved a satisfactory aqueous full

Adv. Funct. Mater. 2020, 2001867 2001867 (7 of 10) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 6. The electrochemical performance of Zn||MnO2 and AEC-Zn||MnO2 cells: a) CV curves at a scanning rate of 0.1 mV s−1 (second cycle),
b) charge/discharge profiles (second cycle), and c) galvanostatic cycling performance at 2 C.
cell with excellent cyclability and high reliability. Considering
the facile and low-cost synthesis, the present AEC-coating
method can provide not only a practical strategy to enable
rechargeable Zn batteries for commercial applications, but
also a fundamental understanding toward dendrite-free metal
electrodeposition.
4. Experimental Section
Preparation of AEC-Zn: PVDF (0.10 g, Mw = 1 000 000) was first
dissolved in NMP (7.78 mL, Sinopharm Chemical) solvent at 60 °C
under magnetic stirring. Then, nanosized TiO2 powders (0.23 g AR,
99.0%, Aladdin) were added to the above solution. After being stirred
for 1 week, a homogeneous slurry was obtained. To prepare AEC-coated
Zn (or Ti) electrode, 30 µL of the as-prepared slurry was drop cast onto
Zn (Φ12, Xingye Metal Materials, 99.9%) or Ti (Φ12, Xingye Metal
Materials) foils, and the resulted electrodes were heated in a vacuum
oven at 40 °C to remove any residual NMP.
Synthesis of MnO2: MnO2 powders were prepared according to the
previous work.[22] In a typical procedure, 1 mL of 0.5 m H2SO4 solution
was added into 45 mL of 0.003 m MnSO4 solution under magnetically
stirring until a transport solution was obtained. Then, 10 mL of 0.1 m
KMnO4 solution was added into the above solution drop by drop. After
being stirred for 2 h, the above mixture was transferred into a Teflon-
lined autoclave and heated at 120 °C for 12 h. Finally, the solid product
was collected by centrifugation, washed with deionized water, and dried
in an oven at 80 °C.
Materials Characterizations: The morphologies of samples were
characterized using a FESEM (Nova NanoSEM 450) equipped with
EDS and an optical microscope equipped with 3D measurement
system provided by Keyence Corporation. The in situ observations
of zinc deposition and exfoliation were carried out on an optical
Adv. Funct. Mater. 2020, 2001867 2001867 (8 of 10)
www.afm-journal.de
microscope (6XB-PC, Optical Instrument Factory), where the zinc
plates (100 mm long, 100 mm wide, and 50 mm high) were fixed
onto a transparent glass plate to construct a homemade optical cell.
XRD patterns were recorded by a Bruker-AXS microdiffractometer
(D8 ADVANCE) with Cu-Kα1 radiation (λ = 1.5406 Å) from 10° to 90°.
The mechanical properties of the PVDF layer and AEC layer were
measured using nanoindentation (iNano, Nanomechanics, Inc., Oak
Ridge, TN, USA). The contact angle between the electrolyte and the
Zn electrode was measured by a contact angle measuring instrument
(JC2000D1, Shanghai Powereach Digital Technology Equipment Co.,
Ltd.).
Electrochemical Measurements: The cathode slurry was prepared by
mixing the MnO2 powder, acetylene black carbon, and PVDF with a
weight ratio of 7:2:1 in NMP solution, and then the slurry was coated
onto a carbon paper. After drying, the carbon paper was cut into circular
sheets with a diameter of 12 mm. The areal mass loading for the MnO2
electrodes was about 1.0 mg cm−2. All the electrochemical performances
were tested with CR2032 coin cells assembled with working and
counter electrodes separated by a glass fiber separator (Φ19). Three
working electrodes were used in this study: bare Zn, AEC-Zn, and MnO2
electrodes. The counter electrodes were either bare Zn or AEC-Zn. The
Zn plating/stripping performance was measured in Zn||Zn (or AEC-
Zn||AEC-Zn) symmetrical cells using 2 m ZnSO4 (100 µL) solution as the
electrolyte. For the long-term cycling, Zn foil with a thickness of 80 µm
and a current density of 0.885 mA cm−2 was used, while for the deep-
discharge tests, the numbers were 25 µm and 8.85 mA cm−2. The CE of
Zn anodes was measured with Zn||Ti (or Zn||AEC-Ti) cells at a current
density of 1.77 mA cm−2 for 0.5 h. The electrochemical performance of full
cells (Zn||MnO2 or AEC-Zn||MnO2) was tested using 2 m ZnSO4+0.1 m
MnSO4 (100 µL) solution as the electrolyte at 2 C in a voltage range of
1.0–1.8 V. All the tests above were performed on a Neware Battery Tester.
The EIS of the symmetrical cells in the frequency range of 0.01–100 kHz
and CV curves of the full cells at a scan rate of 0.1 mV s−1 were recorded
by a BioLogic electrochemistry workstation.
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (grant no. 51802225) and the funding from State
Key Laboratory of Materials Processing and Die & Mould Technology,
Huazhong University of Science and Technology.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
anti-corrosion coating, Zn anodes, Zn electrodeposition, Zn protection,
Zn-ion batteries
Received: February 27, 2020
Revised: April 19, 2020
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