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Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte

Additive for Uniform Zinc Deposition
Kaixuan Xie, Kaixin Ren, Chuang Sun, Shuna Yang, Minman Tong,* Shun Yang, Zhifang Liu,
and Qinghong Wang*
Cite This: ACS Appl. Energy Mater. 2022, 5, 4170−4178 Read Online

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ABSTRACT: Zn-ion batteries are re-evaluated as a potential

choice to address the safety issue and cost concerns of current
energy storage systems. Unfortunately, further application is
severely hindered by low coulombic efficiency and poor cycle
life, which are caused by the undesirable dendrite growth and side
reactions on metal Zn anode. Herein, ethylenediaminetetraacetic
acid (EDTA) is employed as an electrolyte additive to solve the
problem. The functional groups of EDTA adsorption layer on Zn
foil results in refined grains by providing abundant nucleation sites
for initial deposition and further induces uniform and flat Zn
deposition without dendrites. Moreover, the chelation of EDTA
with Zn2+ changes the coordination environment of hydrated Zn2+
and suppresses the side reactions. The smooth deposition of Zn
endows the Zn anodes with super stability in both symmetric cells and Zn−V2O5 full cells. This work provides a simple and feasible
approach for solving anode issues in high-performance and safe Zn-ion batteries.
KEYWORDS: zinc-ion battery, electrolyte additive, grain refinement, anode protection, long cycle life

1. INTRODUCTION The cycling process of the Zn anode involves reversible Zn

Compared with traditional organic electrolyte-based lithium-
ion batteries, rechargeable zinc-ion batteries (ZIBs) possess a
great range of potential applications due to the high safety, low
cost, and an abundance of natural reserves.1,2 Notably, the zinc
(Zn) anode possesses remarkable superiority of high
theoretical capacity (820 mAh g−1) and low redox potential
(−0.76 V vs SHE).3,4 However, further application is limited
by the poor cycling performance and low coulombic efficiency
(CE) caused by the quick failing of the metal Zn anode.5,6
Zn dendrites are prone to generate in the plating process
because the initial Zn nucleation is normally localized, and this
will induce the formation of heterogeneous interfacial electric
field and further result in Zn2+ accumulation on the interfacial
nucleation sites. Subsequently, metallic Zn will continue to
deposit on the former layer due to the “tip effect” and form
protuberances, even lead to short-circuit failure of the cell. The
newly formed dendrites also increase the electrode surface and
trigger a series of side reactions, thus forming undesired “dead”
Zn passivation layer.7,8 To solve these problems, researchers
have made much effort to balance the interfacial electric field
and regulate Zn2+ migration to obtain high-performance Zn
anodes. Accordingly, many effective strategies have been
developed, e.g., structural construction,9,10 surface modifica-
tion,11,12 and electrolyte optimization.13−16
plating/stripping and its durability relies largely on the quality
of the electrodeposition layer.17,18 In the electrodeposition
field, the method of introducing additives into the metal
electroplating bath is commonly used to regulate the
deposition kinetics to obtain flat, bright, and compact coating
layers.19 Cui’s group employed polyamide as an interphase to
regulate the Zn deposition behavior in aqueous media.20
Polyacrylamide was used as an electrolyte additive to achieve a
bright electroplated surface.21 The complexing agent is an ideal
electrolyte additive to control the electroplating process for a
smooth surface by refining the crystal grains.22−24 The
complexing effect generates more activated sites for metal
deposition and reduces the critical radius of the crystal nucleus,
thus resulting in a smaller grain size and inhibiting the
formation of metal dendrites. However, the strategy of refining
grains via complexing agent for the fabrication of a Zn anode
has been rarely investigated.
Received: November 12, 2021
Accepted: March 18, 2022
Published: March 31, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsaem.1c03558

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Figure 1. (a) Schematics and (b) in situ optical microscopic observation of Zn deposition in the electrolytes with/without EDTA; SEM images of
Zn anodes after plated in blank electrolyte for (c, d) 10 min and (e, f) 60 min and in electrolyte with EDTA for (h, i) 10 min and (j, k) 60 min.
AFM images of Zn anodes after plated in (g) blank electrolyte and (l) electrolyte with EDTA for 60 min.
Ethylenediaminetetraacetic acid (EDTA, H4Y) undergoes
strong chelation with metal ions and is usually used as an
electrolyte additive to realize dense and flat deposition of a
metal or alloy.25,26 Inspired by such work, EDTA was used in
this study as an electrolyte additive for uniform Zn deposition
(Figure 1a). The Zn affinity of EDTA and its chelation with
Zn2+ generate more active sites for initial nucleation, resulting
in a smaller grain size during the initial plating stage. In the
subsequent plating process, a flat and compact plating layer
without obvious “dead” Zn is achieved, thus ensuring superior
cycling stability for the Zn anode in EDTA-based electrolyte.
Moreover, the addition of EDTA changes the coordination
environment of Zn2+ and significantly suppresses the side
reactions, thus leading to improved CE.27 Because of these
multiple functions, both of the symmetric cells and full cells
using EDTA-based electrolyte deliver favorable cycling
stability.
2. EXPERIMENTAL SECTION
2.1. Materials Preparation. Preparation of zinc sulfate solution
with EDTA: EDTA (Alfa Aesar) was dissolved into 2 M zinc sulfate
solution with continuous stirring at 70 °C until all the EDTA had
completely dissolved; the concentrations of the EDTA were 0.02,
0.04, and 0.08 M. Correspondingly, the as-obtained electrolytes were
marked as ZSO-EDTA-0.02, ZSO-EDTA-0.04, and ZSO-EDTA-0.08.
2.2. Structural Characterization. The composition analysis were
performed by X-ray diffraction (XRD, Bruker-D8 Advance X-ray
diffractometer, Cu Kα radiation), energy dispersive X-ray spectros-
copy (EDS), and X-ray photoelectron spectroscopy (XPS, Thermo
Fisher K-Alpha system). The XPS depth profiles were collected by
using an Ar+ ion beam, where a raster size of 2 mm and a sputtering
rate of 4 kV were used for different time periods. The morphology
was tested by a scanning electron microscope (SEM, Hitachi SU-
8010). In situ optical microscopic observation was performed with a
NIKON SMZ1270 optical microscope. The roughness was charac-
terized by an atomic force microscope (AFM, Bruker Dimension
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Icon). The contact angle was measured on a Ramé Hart 260 contact
angle goniometer.
2.3. Electrochemical Measurements. The batteries were
assembled in a CR2032 coin cell configuration by using 2 M
ZnSO4 with/without EDTA as electrolytes and glass fiber as
separator. The V2O5 cathode was fabricated by mixing V2O5,
superconducting C, and polytetrafluoroethylene (PTFE) binder in a
weight ratio of 7:2:1 with absolute ethanol as solvent. Then the
resulting sticky material was pressed into thin sheets with a mass
loading of ∼1.0 mg cm−2 and then tailored for use. The
electrochemical performances of the cells were tested on a battery
testing system (LAND, CT2001A). Cyclic voltammetry (CV) and
electrochemical impedance spectroscopy (EIS) tests were performed
on a CHI 660e electrochemical station.
2.4. Calculation Methods. The geometries of the coordination
complexes were optimized in SMD (solvent model based on density)
solvent (water, ε = 78.35) by using B3LYP-D3 and with the 6-31+G*
basis set under standard convergence criteria in the Gaussian 09
package.28,29 The optimized structures were confirmed to be the true
minima from calculations of the analytical vibrational frequencies.30
To calculate accurately the energy of a water molecule, an explicit
model of water molecules which surround a specific water molecule
should be considered. The released water molecules were represented
by a water cluster containing 18 water molecules when calculating the
reaction energies (eq 1).31,32
[Zn(H 2O)6 ]2 + + H4Y + 6(H 2O)18 → [Zn(H4Y)]2 + + 6(H 2O)19
(1)
The formation energy of the complex was calculated as follows:
ΔE = E([Zn(H4Y]2 + ) + E(6(H 2O)19 ) − E([Zn(H 2O)6 ]2 + )
− E(H4Y) − E(6(H 2O)18 )
where E is the ab initio total energy of the unit in the parentheses.
Density functional theory (DFT) calculations were performed to
study the combination between EDTA and Zn board in the DMol3
system. The calculations were based on generalized gradient
approximation (GGA) 33 and the Perdew−Burke−Ernzerhof
(PBE)34 exchange-correlation function. A vacuum slab with the
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Figure 2. (a) Cyclic performance of Zn−Zn symmetric cells at a current density of 1 mA cm−2 and a fixed capacity of 1 mAh cm−2. (b) Ion
conductivity of the ZSO electrolytes with various contents of EDTA. (c) Structure of the [ZnH4EDTA]2+ complex cation. (d) Differential
capacitance curves obtained at 298 K in blank ZSO and electrolytes with EDTA. (e) Contact angle measurements of the electrolytes on a Zn
electrode. (f) EDTA adsorbed on Zn foil and the corresponding binding energy.
thickness of 15 Å was employed for avoiding the interaction between
periodical images and slab. Effective core potentials with a DNP
(double numerical plus polarization) basis set and a DFT-D method
within the transition state structures scheme were used for calculation.
The COSMO model with a dielectric constant of 78.54 was used to
consider the solvent environment of water.
3. RESULTS AND DISCUSSION
The effect of EDTA on Zn deposition was investigated by in
situ monitoring the plating process at 1 mA cm−2 in symmetric
cells. As shown in Figure 1b, the bare Zn electrode exhibits a
smooth surface. After 10 min of deposition in blank ZSO
electrolyte, unevenly distributed protrusions start to sprout on
Zn surface and gradually grow with time. The protrusions will
finally form Zn dendrites with further cycling due to the
“protrusion effect”.35 In contrast, in the electrolyte containing
EDTA, the Zn anode exhibits a smooth edge without the
appearance of dendrites for the whole deposition process.
Additional insight into the surficial morphology of the Zn foil
after plating with and without EDTA as additive was obtained
from characterization studies by SEM. For the blank ZSO
electrolyte, unevenly distributed and irregular protuberances
were observed after plating for 10 min (Figures 1c and 1d);
these protrusions grew larger and disordered as the deposition
time increased (Figures 1e and 1f). It is noted that the Zn
anode became riddled with cracks, further indicating the
inhomogeneous deposition of metallic Zn in the blank ZSO
electrolyte. In contrast, in the electrolyte containing EDTA, a
more dense and smooth plating layer composed of ultrafine
nanocrystals was obtained (Figure 1h−k). Comparison of
Figures 1f and 1k clearly demonstrated that the EDTA additive
can effectively refine the crystal grains and depress the dendrite
growth. The AFM measurements revealed the rough surface of
the Zn anode with isolated dendrites of ∼332 nm in height
after 60 min plating in blank ZSO electrolyte (Figure 1g). In
contrast, a flat plating layer with an altitude intercept of ∼158
nm was obtained for the electrolyte containing EDTA (Figure
1l), further supporting the hypothesis that EDTA can act as a
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refiner for Zn deposition and diminish the tendency for
dendrite growth during cycling.
The effect of EDTA on Zn stripping was also studied by
SEM. Figure S1 shows that the Zn foil after stripping for 1 h at
1 mA cm−2 in blank electrolyte presents a mossy-type surface
with scattered microflakes, indicating the occurrence of side
reactions. In contrast, the anode obtained for the electrolyte
with EDTA exhibits a smooth surface, hence providing a
desired substrate for the following dendrite-free Zn plating.
The galvanostatic cycling performance of Zn anodes in each
electrolyte was evaluated in symmetric cells at the current
density of 1 mA cm−2 with a fixed capacity of 1 mAh cm−2
(Figure 2a). After cycling for 54 h, a sudden drop followed by
voltage fluctuations is observed for the blank ZSO electrolyte
(Figure S2a), indicating a short circuit of the cell, which results
from the piercing of the cell membrane by the accumulated
dendrites.36 The cells with electrolyte containing EDTA
exhibited a more stable polarization voltage and better cycling
stability of 4000 h. As shown in Figure S2b, the cells with
EDTA-based electrolyte displayed higher voltage hysteresis
(∼132.3 mV) than those employing the blank electrolyte
(∼84.8 mV), suggesting a higher energy barrier for metal
nucleation in the former cells. At the same current density, the
high nucleation overpotential can generate an enhanced
driving force for nucleation and produce more nucleation
sites, thus decreasing critical grain size.37−39 Therefore, high
nucleation overpotential may lead to refined nuclei during the
initial deposition process and further lead to dense and smooth
surface for the following deposition process, which clearly will
be of benefit in terms of suppressing dendrite growth.
To reveal the effect mechanism of EDTA electrolyte
additive, various experiments and calculations were carried
out. The pH value of the ZSO-EDTA-0.04 electrolyte was
2.15, and EDTA exists mainly in the form H4Y.40,41 The trend
regarding the complexation strength of EDTA was validated by
calculating the reactions energies (ΔE) for the [ZnH4Y]2+
complex based in eq 1: [Zn(H2O)6]2+ + H4Y + 6(H2O)18 →
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Figure 3. XPS survey spectra of Zn anode after the 10th cycle in EDTA-based electrolyte: (a) Full survey XPS spectra at various Ar+ sputtering
times. High-resolution XPS spectra of (b) C 1s and (c) N 1s before etching. XPS depth profiles of (d) C 1s, (e) N 1s, and (f) Zn 2p at various Ar+
sputtering times.

Figure 4. Long-term galvanostatic cycling of the symmetric cells at the current density and capacity of (a) 2 mA cm−2, 2 mAh cm−2 and (c) 4 mA
cm−2, 4 mAh cm−2. Coulombic efficiencies for the Zn plating/stripping process at (b) 2 mA cm−2, 2 mAh cm−2 and (d) 4 mA cm−2, 4 mAh cm−2.
(e) Comparison of the cycling performances for Zn anodes in EDTA containing electrolytes with previously reported electrolytes with different
additives.

[Zn(H4Y)]2+ + 6(H2O)19. According to DFT, ΔE was
calculated as −1.56 eV, demonstrating that the [ZnH4Y]2+
complex is more stable than solvated [Zn(H2O)6]2+ (Figure
2c). The substitution of H2O by EDTA may effectively inhibit
the chemical corrosion of electrolyte on the Zn anode. The
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blocking effect of complexation also inhibits the diffusion of
Zn2+ to the interface, which is confirmed by the sluggish ion
mobility of the electrolytes containing EDTA as additive
(Figure 2b) and the increased charge transfer resistance of the
symmetric cells (Figure S3). Moreover, the stronger binding
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Figure 5. Cross-section and surface morphology of Zn anodes cycled for 100 h in (a, d) ZSO electrolyte and (b, e) ZSO electrolyte with EDTA,
and (c, f) after cycling for 500 h in electrolyte with EDTA.
affinity of Zn2+ with H4Y compared to H2O makes it more
difficult to break the solvation sheath with respect to the
reduction of Zn2+, thus leading to an increased nucleation
overpotential.42
The adsorption of EDTA on Zn foil was verified by
differential capacitance measurements. As shown in Figure 2d,
the capacitance for the electrolyte systems containing EDTA
was much lower than that for the blank ZSO electrolyte. When
the concentration of EDTA was 0.04 mol L−1, the electrode
presented the lowest capacitance, indicating that saturation was
achieved for the adsorption of EDTA on the Zn anode.
Contact angle measurements indicated that the electrolytes
with EDTA had an enhanced affinity for Zn (Figure 2e). DFT
calculations also revealed that the functional groups of EDTA
endowed the EDTA on the Zn foil with a good adsorption
capability (Figure 2f), thus ensuring an abundance of activated
sites that would contribute to the generation of refined
nucleation grains with good uniformity.43 Moreover, foreign
adsorbed molecules on the surface of electrode can improve
the activation energy for adatoms diffusion, thus restraining the
2D surfacial ion diffusion, which may lead to dendrite
growth.17
XPS measurements were conducted to provide additional
evidence for the effects of EDTA on the Zn anode. In the full
survey spectra (Figure 3a), C, O, Zn, and S were clearly
detected for the electrode after 10 cycles. The high-resolution
C 1s spectra present typical bonds for C−H, C−C, C−O/C−
N, and CO at 284.2, 284.9, 285.4, and 289.4 eV, respectively
(Figure 3b). The presence of N in the full survey spectra is not
clear, but from the high-resolution spectra, the typical bonds
for N−C (399.4 eV) and N−H (402.5 eV) associated with N
1s are evident (Figure 3c).
The above results all point to the existence of EDTA on the
Zn surface. In an additional experiment, Ar+ sputtering was
undertaken in an attempt to characterize the different depths
of the deposition layer. When the sputtering times increased to
500 and 1000 s, the intensities of the C 1s (Figure 3d) and N
1s (Figure 3e) peaks gradually decreased and eventually
disappeared, while those for Zn 2p gradually increased (Figure
3f), indicating that the mass concentration of EDTA on the
surface was higher than in the internal deposition layers. It can
be confirmed that EDTA was indeed absorbed on Zn anode.
The absorbed EDTA may also act as a leveling agent because
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most organic molecules are preferentially adsorbed on the
protrusions of electrode and hinder the robust deposition of
Zn.
To optimize the concentration of the electrolyte additive,
the electrochemical stability of Zn foil in various EDTA-based
electrolytes was evaluated by galvanostatic cycling (Figure 4a).
Obviously, the Zn anode exhibits enhanced cycling stability in
the EDTA added electrolytes. In ZSO-EDTA-0.04 electrolyte,
it presents the best reversibility of 3000 h (1500 cycles) at 2
mA cm−2 with an areal capacity of 2 mAh cm−2, superior to the
poor performance (failure after ∼60 h) in blank ZSO
electrolyte. Concentrations lower or higher than 0.04 M
exhibited relatively poor cycling stability. This may have been
because at the lower concentrations the incomplete complex-
ing of Zn2+ and the partly covered Zn foil cannot effectively
control the nucleation process. Conversely, for increased
EDTA concentrations, the overpotential is increased, benefit-
ing for dendrite-free Zn deposition. However, excessive
concentrations cause sluggish ion mobility, thus deteriorating
the cycling performance. The electrochemical properties of the
cells with EDTA were further evaluated at higher current
densities. As shown in Figure 4c, long-term stability for 1600 h
is realized with the plating capacity of 4 mAh cm−2, this value
being about 10 times that for the blank ZSO electrolyte, thus
further confirming the improvement of cycling stability with
EDTA as additive. The comparison data shown in Figure 4e
and Table S1 indicate that Zn anodes exhibit enhanced and
stable cycling performance for electrolytes with EDTA in
comparison to most previously optimized electro-
lytes.15,21,42,44−55
The CE of Zn plating/stripping in ZSO-EDTA-0.04
electrolyte was measured to evaluate the practicality of the
electrolyte additive. As shown in Figure S4, Figure 4b, and
Figure 4d, unlike the fluctuating CEs in blank ZSO electrolyte,
more stable CEs with average values of 99.36%, 99.68%, and
99.87% were obtained at 1, 2, and 4 mA cm−2, respectively, for
the Cu−Zn cell in ZSO-EDTA-0.04 electrolyte. These high
values can be attributed to the impression of dendrite growth
and side reactions. As shown in the ex situ XRD patterns
(Figure S5), characteristic peaks for Zn(OH)2 (JCPDS No. 38-
385) and Zn4SO4(OH)6 (JCPDS No. 39-689) can clearly be
seen for the Zn anode extracted from the blank ZSO
electrolyte after 10 cycles, which are not observed in the
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Figure 6. Electrochemical properties of the Zn−V2O5 full cells: (a) CV curves measured at a scan rate of 0.05 mV s−1. (b) Rate performance
measured from 0.2 to 2 A g−1. (c) Voltage profiles of the cell in EDTA-based electrolyte at a current density of 2 A g−1 for different cycles. (d)
Cycling performance of the full cells at a current density of 2 A g−1.
electrolytes with EDTA, indicating that the formation of
inactive byproducts is greatly suppressed by EDTA. The
formation of the characteristic peaks for Zn(OH)2 and
Zn4SO4(OH)6 can be attributed to the transformation of the
solvation configuration around Zn2+, which may retard the
occurrence of side reactions,27,56 thus contributing to the high
CE values.
To further confirm the effect of EDTA on Zn deposition,
surficial morphology change of the electrode after long-term
plating/stripping was studied by SEM. As shown in Figures 5a
and 5d, after 100 h cycling at 1 mA cm−2, the Zn anode in
blank ZSO electrolyte exhibited a rough surface composed of
massive flake-like byproducts with a thickness of ∼10 μm, thus
demonstrating severe corrosion from the surface to the
interior, while the cycled electrode in EDTA-based electrolyte
exhibited a dense and flat surface without protrusions or cracks
(Figures 5b and 5e). Even after cycling for 500 h, the anode
presented no obvious changes in morphology (Figures 5c and
5f). The compact Zn film may contribute to the improved
charge transfer of the cells by using EDTA additive (Figure
S6). This confirmed that EDTA can effectively regulate
nucleation and inhibit dendrite growth even after long-term
cycling. The uniform elemental distribution (Figure S7) of the
Zn anode after 500 h further indicates the adsorption of
EDTA. Therefore, EDTA can regulate Zn deposition over a
long time period.
The practical utility of the electrolytes containing EDTA was
studied by evaluating the performance of hybrid Zn−V2O5 full
cells. The CV curves (Figure 6a) of the cells presented two
pairs of redox peaks at 0.75, 0.6 V and 1.0, 0.8 V, respectively,
indicating the two-step insertion/extraction of Zn2+ in
V2O5.57,58 Clearly, for the electrolyte with EDTA, the cathodic
peaks shift in a negative direction, and the anodic peaks shift
positively slightly compared with those obtained in blank ZSO
electrolyte, indicating the improved electrochemical kinetics in
the presence of EDTA. The rate performance measurements
(Figure 6b) show that the cell using EDTA-based electrolyte
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delivers a high and stable CE approaching 100% and high
average specific capacities of 368, 354, 315, and 258 mAh g−1
at various current densities of 0.2, 0.5, 1.0, and 2.0 A g−1,
respectively. The improved rate performance in EDTA-based
electrolyte may be attributed to the suppressed dendrite
growth and side reactions, which could contribute to the
improved charge transfer kinetics of the Zn anode. The
charge/discharge curves of the cells display two pairs of
charge/discharge plateaus (Figure 6c), agreeing well with the
CV curves. The long-term cycling stability was further
measured at various current densities. At a current density of
1 A g−1, the cell with EDTA additive displays a high discharge
capacity of 310.2 mAh g−1 and maintains 217.4 mAh g−1 at the
500th cycle (Figure S8). At a higher current density of 2 A g−1
(Figure 6d), both of the cells show high CE values of nearly
100%. Moreover, a high reversible capacity of 199.7 mAh g−1
was obtained for the electrolyte with EDTA after 500 cycles,
demonstrating good cycling stability. However, much more
severe fading of the capacity occurred for the cell with the
blank ZSO electrolyte, which may result from the serious
passivation and dendrite growth of the Zn anode. The cycling
performance of the cell with higher V2O5 mass loading of 5.0
mg cm−2 is shown in Figure S9. The cell with EDTA-based
electrolyte delivers a high initial capacity of 320.3 mAh g−1 at
the current density of 1 A g−1 and still remains at 140.5 mAh
g−1 after 100 cycles.
4. CONCLUSIONS
A simple and effective strategy for stable Zn anode, based on
the use of EDTA electrolyte additive, has been demonstrated.
On one hand, the strong chelation between EDTA and Zn2+
extends polarization during the initial deposition process and
generates more nucleation sites, thus refining the crystal grains
and inducing uniform Zn deposition. On the other hand, the
adsorption of EDTA on Zn foil also contributes to the uniform
deposition. Moreover, the transformation of the solvation
configuration of Zn2+ helps to suppress side reactions. The
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symmetric cell delivers a high CE of 99.36% and long cycle life
of 4000 h in the ZSO electrolyte containing 0.04 M EDTA.
The Zn−V2O5 battery also displays good performance in terms
of improved rate capability (258 mAh g−1 at 2 A g−1) and long-
term cycling stability (199.7 mAh g−1 after 500 cycles at 2 A
g−1).
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.1c03558.
Figures showing the structure of Zn anodes after initial
stripping, voltage profiles, EIS plots, and long-term
galvanostatic cycling of Zn−Zn symmetric cells,
Coulombic efficiency measurements of Cu−Zn cells,
morphology, crystal structure, and EIS plots of cycled
Zn−Zn symmetric cells (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Minman Tong − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China; orcid.org/0000-0002-9357-5684;
Email: tongmm@jsnu.edu.cn
Qinghong Wang − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China; orcid.org/0000-0003-0432-0741;
Email: wangqh@jsnu.edu.cn
Authors
Kaixuan Xie − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China
Kaixin Ren − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China
Chuang Sun − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China
Shuna Yang − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China
Shun Yang − School of Chemistry and Materials Science,
Jiangsu Key Laboratory of Green Synthetic Chemistry for
Functional Materials, Jiangsu Normal University, Xuzhou
221116, P. R. China
Zhifang Liu − Institute of Biopharmaceutical Research,
Liaocheng University, Liaocheng 252059, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c03558
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
This work was supported by Natural Science Foundation of
Jiangsu Province (No. BK20211352) and the Postgraduate
Research & Practice Innovation Program of Jiangsu Province
(No. KYCX20_2241).
■
REFERENCES
(1) Wang, F.; Borodin, O.; Gao, T.; Fan, X.; Sun, W.; Han, F.;
Faraone, A.; Dura, J. A.; Xu, K.; Wang, C. Highly reversible zinc metal
anode for aqueous batteries. Nat. Mater. 2018, 17 (6), 543−549.
(2) Song, M.; Tan, H.; Chao, D.; Fan, H. J. Recent Advances in Zn-
ion Batteries. Adv. Funct. Mater. 2018, 28 (41), 1802564.
(3) Li, Y.; Lu, J. Metal-air batteries: will they be the future
electrochemical energy storage device of choice? ACS Energy Lett.
2017, 2 (6), 1370−1377.
(4) Sun, G.; Yang, H.; Zhang, G.; Gao, J.; Jin, X.; Zhao, Y.; Jiang, L.;
Qu, L. A capacity recoverable zinc-ion micro-supercapacitor. Energy
Environ. Sci. 2018, 11 (12), 3367−3374.
(5) Li, C.; Xie, X.; Liang, S.; Zhou, J. Issues and future perspective
on Zinc metal anode for rechargeable aqueous Zinc-ion batteries.
Energy Environ. Sci. 2020, 3 (2), 146−159.
(6) Yang, Q.; Liang, G.; Guo, Y.; Liu, Z.; Yan, B.; Wang, D.; Huang,
Z.; Li, X.; Fan, J.; Zhi, C. Do Zinc dendrites exist in neutral Zinc
batteries: A developed electrohealing strategy to in situ rescue in-
service batteries. Adv. Mater. 2019, 31 (43), 1903778.
(7) Liu, Z.; Cui, T.; Pulletikurthi, G.; Lahiri, A.; Carstens, T.;
Olschewski, M.; Endres, F. Dendrite-free nanocrystalline Zinc
electrodeposition from an ionic liquid containing nickel triflate for
rechargeable Zn-based batteries. Angew. Chem., Int. Ed. Engl. 2016, 55
(8), 2889−2893.
(8) Li, M.; He, Q.; Li, Z.; Li, Q.; Zhang, Y.; Meng, J.; Liu, X.; Li, S.;
Wu, B.; Chen, L.; Liu, Z.; Luo, W.; Han, C.; Mai, L. A novel dendrite-
free Mn2+/Zn2+ hybrid battery with 2.3 V voltage window and 11000-
cycle lifespan. Adv. Energy Mater. 2019, 9 (29), 1901469.
(9) Yu, J.; Chen, F.; Tang, Q.; Gebremariam, T. T.; Wang, J.; Gong,
X.; Wang, X. Ag-modified Cu foams as three-dimensional anodes for
rechargeable Zinc-air batteries. ACS Appl. Nano Mater. 2019, 2 (5),
2679−2688.
(10) Shi, X.; Xu, G.; Liang, S.; Li, C.; Guo, S.; Xie, X.; Ma, X.; Zhou,
J. Homogeneous deposition of zinc on three-dimensional porous
copper foam as a superior zinc metal anode. ACS Sustain. Chem. Eng.
2019, 7 (21), 17737−17746.
(11) Zheng, J.; Zhao, Q.; Tang, T.; Yin, J.; Quilty, C. D.; Renderos,
G. D.; Liu, X.; Deng, Y.; Wang, L.; Bock, D. C.; et al. Reversible
epitaxial electrodeposition of metals in battery anodes. Science 2019,
366 (6465), 645−648.
(12) Deng, C.; Xie, X.; Han, J.; Tang, Y.; Gao, J.; Liu, C.; Shi, X.;
Zhou, J.; Liang, S. A sieve-functional and uniform-Porous kaolin layer
toward stable Zinc metal anode. Adv. Funct. Mater. 2020, 30 (21),
2000599.
(13) Chen, Z.; Tang, Y.; Du, X.; Chen, B.; Lu, G.; Han, X.; Zhang,
Y.; Yang, W.; Han, P.; Zhao, J.; Cui, G. Anion solvation
reconfiguration enables high-voltage carbonate electrolytes for stable
Zn/graphite cells. Angew. Chem., Int. Ed. Engl. 2020, 59 (48), 21769−
21777.
(14) Zhang, Y.; Li, H.; Huang, S.; Fan, S.; Sun, L.; Tian, B.; Chen,
F.; Wang, Y.; Shi, Y.; Yang, H. Y. Rechargeable aqueous Zinc-ion
batteries in MgSO4/ZnSO4 hybrid electrolytes. Nanomicro Lett. 2020,
12 (1), 60.
(15) Xu, W.; Zhao, K.; Huo, W.; Wang, Y.; Yao, G.; Gu, X.; Cheng,
H.; Mai, L.; Hu, C.; Wang, X. Diethyl ether as self-healing electrolyte
additive enabled long-life rechargeable aqueous zinc ion batteries.
Nano Energy 2019, 62, 275−281.
(16) Shen, Y.; Liu, B.; Liu, X.; Liu, J.; Ding, J.; Zhong, C.; Hu, W.
Water-in-salt electrolyte for safe and high-energy aqueous battery.
Energy Storage Mater. 2021, 34, 461−474.
https://doi.org/10.1021/acsaem.1c03558
ACS Appl. Energy Mater. 2022, 5, 4170−4178
ACS Applied Energy Materials
(17) Dong, J.; Dai, H.; Fan, Q.; Lai, C.; Zhang, S. Grain refining
mechanisms: Initial levelling stage during nucleation for high-stability
lithium anodes. Nano Energy 2019, 66, 104128.
(18) Huang, Z.; Zhou, G.; Lv, W.; Deng, Y.; Zhang, Y.; Zhang, C.;
Kang, F.; Yang, Q.-H. Seeding lithium seeds towards uniform lithium
deposition for stable lithium metal anodes. Nano Energy 2019, 61,
47−53.
(19) Aaboubi, O.; Douglade, J.; Abenaqui, X.; Boumedmed, R.;
VonHoff, J. Influence of tartaric acid on zinc electrodeposition from
sulphate bath. Electrochim. Acta 2011, 56 (23), 7885−7889.
(20) Zhao, Z.; Zhao, J.; Hu, Z.; Li, J.; Li, J.; Zhang, Y.; Wang, C.;
Cui, G. Long-life and deeply rechargeable aqueous Zn anodes enabled
by a multifunctional brightener-inspired interphase. Energy Environ.
Sci. 2019, 12 (6), 1938−1949.
(21) Zhang, Q.; Luan, J.; Fu, L.; Wu, S.; Tang, Y.; Ji, X.; Wang, H.
The three-dimensional dendrite-free Zinc anode on a copper mesh
with a Zinc-oriented polyacrylamide electrolyte additive. Angew.
Chem., Int. Ed. Engl. 2019, 58 (44), 15841−15847.
(22) Vangapally, N.; Gaffoor, S. A.; Martha, S. K. Na2EDTA
chelating agent as an electrolyte additive for high performance lead-
acid batteries. Electrochim. Acta 2017, 258, 1493−1501.
(23) Vaghefinazari, B.; Höche, D.; Lamaka, S. V.; Snihirova, D.;
Zheludkevich, M. L. Tailoring the Mg-air primary battery perform-
ance using strong complexing agents as electrolyte additives. J. Power
Sources 2020, 453, 227880.
(24) Chai, L.; Xiong, C.; Zeng, W.; Wu, L.; Hu, H. The role of
chelators in electrodeposition of Cu-As alloys from copper electrolyte.
Jom 2020, 72 (11), 3876−3886.
(25) Barros, K. S.; Ortega, E. M.; Perez-Herranz, V.; Espinosa, D. C.
R. Evaluation of brass electrodeposition at RDE from cyanide-free
bath using EDTA as a complexing agent. J. Electroanal. Chem. 2020,
865, 114129.
(26) Fashu, S.; Gu, C.-d.; Zhang, J.-l.; Huang, M.-l.; Wang, X.-l.; Tu,
J.-p. Effect of EDTA and NH4Cl additives on electrodeposition of Zn-
Ni films from choline chloride-based ionic liquid. T. Nonferr. Metal.
Soc. 2015, 25 (6), 2054−2064.
(27) Cao, Z.; Zhuang, P.; Zhang, X.; Ye, M.; Shen, J.; Ajayan, P. M.
Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc
Ion Batteries. Adv. Energy Mater. 2020, 10 (30), 2001599.
(28) Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the damping
function in dispersion corrected density functional theory. J. Comput.
Chem. 2011, 32 (7), 1456−1465.
(29) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal
solvation model based on solute electron density and on a continuum
model of the solvent defined by the bulk dielectric constant and
atomic surface tensions. J. Phys. Chem. B 2009, 113 (18), 6378−6396.
(30) Hernández-Burgos, K.; Burkhardt, S. E.; Rodríguez-Calero, G.
G.; Hennig, R. G.; Abruña, H. D. Theoretical studies of carbonyl-
based organic molecules for energy storage applications: The
heteroatom and substituent effect. J. Phys. Chem. C 2014, 118 (12),
6046−6051.
(31) Su, J. T.; Xu, X.; Goddard, W. A. Accurate energies and
structures for large water clusters using the X3LYP hybrid density
functional. J. Phys. Chem. A 2004, 108, 10518−10526.
(32) Kelley, M. P.; Bessen, N. P.; Su, J.; Urban, M.; Sinkov, S. I.;
Lumetta, G. J.; Batista, E. R.; Yang, P.; Shafer, J. C. Revisiting
complexation thermodynamics of transplutonium elements up to
einsteinium. Chem. Commun. 2018, 54 (75), 10578−10581.
(33) Perdew, J. P.; Ruzsinszky, A.; Csonka, G. I.; Vydrov, O. A.;
Scuseria, G. E.; Constantin, L. A.; Zhou, X.; Burke, K. Restoring the
density-gradient expansion for exchange in solids and surfaces. Phys.s
Rev. Lett. 2008, 100 (13), 136406.
(34) Sancho-García, J. C.; Brédas, J. L.; Cornil, J. Assessment of the
reliability of the Perdew−Burke−Ernzerhof functionals in the
determination of torsional potentials in π-conjugated molecules.
Chem. Phys. Lett. 2003, 377 (1−2), 63−68.
(35) Hao, J.; Li, B.; Li, X.; Zeng, X.; Zhang, S.; Yang, F.; Liu, S.; Li,
D.; Wu, C.; Guo, Z. An in-depth study of Zn metal surface chemistry
4177
www.acsaem.org Article
for advanced aqueous Zn-ion batteries. Adv. Mater. 2020, 32 (34),
2003021.
(36) Guo, L.; Guo, H.; Huang, H.; Tao, S.; Cheng, Y. Inhibition of
Zinc dendrites in Zinc-based flow batteries. Front. Chem. 2020, 8, 557.
(37) Li, G.; Liu, Z.; Huang, Q.; Gao, Y.; Regula, M.; Wang, D.;
Chen, L.-Q.; Wang, D. Stable metal battery anodes enabled by
polyethylenimine sponge hosts by way of electrokinetic effects. Nat.
Energy 2018, 3 (12), 1076−1083.
(38) Oniciu, L.; Mureşan, L. Some fundamental aspects of levelling
and brightening in metal electrodeposition. J.appl. electrochem. 1991,
21 (7), 565−574.
(39) Ganne, F.; Cachet, C.; Maurin, G.; Wiart, R.; Chauveau, E.;
Petitjean, J. Impedance spectroscopy and modelling of zinc deposition
in chloride electrolyte containing a commercial additive. J. appl.
Electrochem. 2000, 30 (6), 665−673.
(40) Stankovic, S.; Grgur, B.; Krstajic, N.; Vojnovic, M. The kinetics
of the hydrogen evolution reaction on zinc in EDTA solutions in the
pH 3−10 range. J. Electroanal. Chem. 2003, 549, 37−47.
(41) Noorhasan, N. N.; Sharma, V. K. Kinetics of the reaction of
aqueous iron(vi) (FeVIO42‑) with ethylenediaminetetraacetic acid.
Dalton Trans. 2008, No. 14, 1883−1887.
(42) Qin, R.; Wang, Y.; Zhang, M.; Wang, Y.; Ding, S.; Song, A.; Yi,
H.; Yang, L.; Song, Y.; Cui, Y.; Liu, J.; Wang, Z.; Li, S.; Zhao, Q.; Pan,
F. Tuning Zn2+ coordination environment to suppress dendrite
formation for high-performance Zn-ion batteries. Nano Energy 2021,
80, 105478.
(43) Tu, X.; Zhang, Y.; Wang, D.; An, M.; Liu, A.; Zhang, J.; Yang,
P. Influence of composite additive on gold electrodeposition in
DMH-based electrolyte: Combined experimental and theoretical
study. J. Electrochem. Soc. 2020, 167 (2), 022506.
(44) Sun, C.; Wu, C.; Gu, X.; Wang, C.; Wang, Q. Interface
engineering via Ti3C2Tx MXene electrolyte additive toward dendrite-
free Zinc deposition. Nanomicro Lett. 2021, 13 (1), 89.
(45) Bayaguud, A.; Luo, X.; Fu, Y.; Zhu, C. Cationic Surfactant-type
electrolyte additive enables three-dimensional dendrite-free Zinc
anode for stable Zinc-ion batteries. ACS Energy Lett. 2020, 5 (9),
3012−3020.
(46) Hao, J.; Long, J.; Li, B.; Li, X.; Zhang, S.; Yang, F.; Zeng, X.;
Yang, Z.; Pang, W. K.; Guo, Z. Toward High-performance hybrid Zn-
based batteries via deeply understanding their mechanism and using
electrolyte additive. Adv. Funct. Mater. 2019, 29 (34), 1903605.
(47) Liu, Y.; Shi, Q.; Wu, Y.; Wang, Q.; Huang, J.; Chen, P. Highly
efficient dendrite suppressor and corrosion inhibitor based on gelatin/
Mn2+ Co-additives for aqueous rechargeable zinc-manganese dioxide
battery. Chem. Eng. J. 2021, 407, 127189.
(48) Guo, X.; Zhang, Z.; Li, J.; Luo, N.; Chai, G.-L.; Miller, T. S.;
Lai, F.; Shearing, P.; Brett, D. J. L.; Han, D.; Weng, Z.; He, G.; Parkin,
I. P. Alleviation of dendrite formation on Zinc anodes via electrolyte
additives. ACS Energy Lett. 2021, 6 (2), 395−403.
(49) Hou, Z.; Dong, M.; Xiong, Y.; Zhang, X.; Ao, H.; Liu, M.; Zhu,
Y.; Qian, Y. A high-energy and long-life aqueous Zn/birnessite battery
via reversible water and Zn2+ coinsertion. Small 2020, 16 (26),
2001228.
(50) Zhang, N.; Cheng, F.; Liu, Y.; Zhao, Q.; Lei, K.; Chen, C.; Liu,
X.; Chen, J. Cation-deficient spinel ZnMn2O4 cathode in Zn-
(CF3SO3)2 electrolyte for rechargeable aqueous Zn-ion battery. J.
Am. Chem. Soc. 2016, 138 (39), 12894−12901.
(51) Naveed, A.; Yang, H.; Yang, J.; Nuli, Y.; Wang, J. Highly
Reversible and rechargeable safe Zn batteries based on a triethyl
phosphate electrolyte. Angew. Chem. Int. Ed. Engl. 2019, 58 (9),
2760−2764.
(52) Li, D.; Cao, L.; Deng, T.; Liu, S.; Wang, C. Design of a Solid
electrolyte interphase for aqueous Zn batteries. Angew. Chem., Int. Ed.
Engl. 2021, 60 (23), 13035−13041.
(53) Chen, P.; Yuan, X.; Xia, Y.; Zhang, Y.; Fu, L.; Liu, L.; Yu, N.;
Huang, Q.; Wang, B.; Hu, X.; Wu, Y.; Ree, T. V. An artificial
polyacrylonitrile coating layer confining Zinc dendrite growth for
highly reversible aqueous Zinc-based batteries. Adv. Sc. 2021, 8 (11),
2100309.
https://doi.org/10.1021/acsaem.1c03558
ACS Appl. Energy Mater. 2022, 5, 4170−4178
ACS Applied Energy Materials www.acsaem.org Article

(54) Hieu, L. T.; So, S.; Kim, I. T.; Hur, J. Zn anode with flexible β-
PVDF coating for aqueous Zn-ion batteries with long cycle life. Chem.
Eng. J. 2021, 411, 128584.
(55) Ma, L.; Chen, S.; Li, X.; Chen, A.; Dong, B.; Zhi, C. Liquid-free
all-solid-state Zinc batteries and encapsulation-free flexible batteries
enabled by in situ constructed polymer electrolyte. Angew. Chem., Int.
Ed. Engl. 2020, 59 (52), 23836−23844.
(56) Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S. The impact of
pH on side reactions for aqueous redox flow batteries based on
nitroxyl radical compounds. J. Power Sources 2016, 321, 126−134.
(57) Ghosh, M.; Vijayakumar, V.; Kurungot, S. Dendrite growth
suppression by Zn2+-integrated nafion ionomer membranes: Beyond
porous separators toward aqueous Zn/V2O5 batteries with extended
cycle life. Energy Technol. 2019, 7 (9), 1900442.
(58) Ding, J.; Du, Z.; Gu, L.; Li, B.; Wang, L.; Wang, S.; Gong, Y.;
Yang, S. Ultrafast Zn2+ intercalation and deintercalation in vanadium
dioxide. Adv. Mater. 2018, 30 (26), 1800762.

4178 https://doi.org/10.1021/acsaem.1c03558
ACS Appl. Energy Mater. 2022, 5, 4170−4178