Multifunctional zinc silicate coating layer for high-performance aqueous zinc-ion batteries

W4406186314 · 수집 2026-09-26 12:33:05

T11690 Advanced battery technologies researchT10281 Advanced Battery Materials and Technologies 이차전지solid state

CoT 라벨링

라벨링 전

PDF 파일

자동 다운로드한 PDF PDF 보기

기본 정보

DOI 제목 발행년도 저널 URL 페이지 열기 PDF URL PDF 열기 발행기관 피인용수 라이선스

추가 정보 초록 본문

## Wang et al. Energy Mater. 2025, 5, 500012 Energy Materials

DOI: 10.20517/energymater.2024.51

Article Open Access

# Multifunctional zinc silicate coating layer for high- performance aqueous zinc-ion batteries

1, Hong Jin2,*, Hui Qiao3,*, Aaron Hardy1, Thomas Schuelke1, Qi Hua Fan4,*

Keliang Wang

1,* , Nina Baule

1Fraunhofer USA, Inc. Center for Midwest, East Lansing, MI 48824, USA.
2Suzhou Research Institute, Xi’an Jiaotong University, Suzhou 215123, Jiangsu, China.
3Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi 214122, Jiangsu, China.
4Department of Electrical Engineering and Computer Engineering & Department of Chemical Engineering and Materials Science,
Michigan State University, East Lansing, MI 48824, USA.

Correspondence to: Dr. Keliang Wang, Fraunhofer USA, Inc. Center for Midwest, East Lansing, Michigan 48824, USA. E-mail:

kwang@fraunhofer.org; Dr. Hong Jin, Suzhou Research Institute, Xi’an Jiaotong University, Suzhou 215123, Jiangsu, China. E-mail:

jhjinhong@mail.xjtu.edu.cn; Prof. Hui Qiao, Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi

214122, Jiangsu, China. E-mail: huiqiao@jiangnan.edu.cn; Prof. Qi Hua Fan, Department of Electrical Engineering and Computer

Engineering & Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, MI 48824,

USA. E-mail: qfan@msu.edu

How to cite this article: Wang, K.; Baule, N.; Jin, H.; Qiao, H.; Hardy, A.; Schuelke, T.; Fan, Q. H. Multifunctional zinc silicate

coating layer for high-performance aqueous zinc-ion batteries. _Energy Mater._ 2025, _5_ [, 500012. https://dx.doi.org/10.20517/](https://dx.doi.org/10.20517/energymater.2024.51)

[energymater.2024.51](https://dx.doi.org/10.20517/energymater.2024.51)

Received: 24 May 2024 First Decision: 18 Jun 2024 Revised: 28 Jun 2024 Accepted: 16 Jul 2024 Published: 8 Jan 2025

Academic Editor: Jiazhao Wang Copy Editor: Ping Zhang Production Editor: Ping Zhang

Abstract

Dendrite growth during the continuous charge/discharge process is a serious problem that leads to internal short

circuits in aqueous zinc-ion batteries. Herein, a multifunctional zinc silicate polymer lithium polysilicate (LSO) was

proposed to address the issues. LSO can prevent direct contact between electrolytes and zinc anodes, thereby

suppressing severe dendrite growth. Its mechanically stable structure can restrain the stress release to further

stabilize the electrode. In addition, LSO is chemically bonded to zinc anodes to ensure superior overall stability

compared to other surface coatings. Moreover, LSO anodes exhibit outstanding electrolyte wettability and

corrosion resistance, with strong adhesion properties. _In-situ_ optical microscopy observation demonstrates its

stability during charge/discharge process. Symmetrical cells using the Zn-LSO anode exhibited long cycling life of

833, 455, 344, and 260 h with low overpotentials of 66, 80, 118, and 141 mV at current densities of 0.5, 1, 3 and 5
mA cm-2, respectively. Full cells coupled with a MnO2 cathode showed a high-capacity reversibility of up to 234

mAh g-1 and outstanding rate performance at different current densities. This study demonstrates that LSO coating

is a promising method for enhancing the electrochemical performance of zinc-ion batteries.

Keywords: Dendrite-free, zinc-ion battery, zinc silicate polymer, multifunctional, high-performance

© The Author(s) 2025. Open Access This article is licensed under a Creative Commons Attribution 4.0
[International License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, sharing,](https://creativecommons.org/licenses/by/4.0/)
adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as
long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and
indicate if changes were made.

[www.oaepublish.com/energymater](https://www.oaepublish.com/energymater)

Page 2 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

## INTRODUCTION

Rechargeable lithium-ion and lithium-metal batteries have achieved remarkable energy/power density and
charge/discharge performance in recent years [1,2] . While improving the operation safety of these batteries is
under active research, the cost and source of the electrode materials remain a concern. Aqueous
rechargeable batteries, including Zn 2+, Mg 2+, Ca 2+, and Al 3+, are promising alternatives. These batteries use
materials that are abundant and environmentally friendly and have achieved considerable power density at a
low cost [3-6] . Furthermore, the neutral electrolyte (pH = 7) has excellent ionic conductivity and the battery
fabrication can be performed in an atmosphere environment, which is particularly advantageous over
sensitive organic-electrolyte-based batteries. Among aqueous rechargeable batteries, zinc-ion batteries with
a zinc metal anode possess unique characteristics and are particularly attractive because of their high
theoretical capacity of 820 mAh g -1, relatively low electrochemical potential [-0.762 V _vs._ standard hydrogen
electrode (SHE)], and highly operational safety [7-9] .

Recently, various metallic Zn-based anode battery systems, such as Zn/Manganese oxide, Zn/Vanadium
oxide, and Zn/hexacyanoferrates [10-13], have demonstrated excellent electrochemical performance. However,
the reported aqueous zinc-ion batteries suffer from a limited life span and considerable capacity fading due
to dendrite growth on the Zn anode during Zn plating/stripping as the batteries charge/discharge [14-17] . Zinc
dendrites not only cause internal short circuits by piercing the separator, but also reduce the utilization of
Zn [15,18,19] . Therefore, achieving a dendrite-free Zn anode is crucial for maintaining stable reversibility in
rechargeable Zn batteries.

The growth of zinc dendrites includes two steps: nucleation and subsequent crystal growth driven by an
electric field. These two steps are determined by the nucleation overpotential and plateau overpotential
during the Zn plating process. Lower overpotential reduces the resistance during nucleation and growth
processes, improving zinc plating quality with less energy consumption [20,21] . These overpotentials are closely
linked to the ion distribution and electric field at the reaction interface. Therefore, considerable efforts have
been devoted to tuning the electron or ion behavior to achieve a dendrite-free Zn anode from the
perspectives of intrinsic Zn anodes, electrolytes, and current collectors. Reported work can be categorized
into three groups: (i) deposit a protective layer [e.g _.,_ AgF/polyvinyl alcohol (PVA), nanoporous CaCO3,
nano‐ZrO2, or polyamide layers] [21-26] on a bare Zn to suppress the Zn evolution; (ii) add an additive to the
electrolyte {e.g _.,_ LiCl, Na2SO4, Zinc (II) bis(trifluoromethylsulfonyl)imide [Zn(TFSI)2] and Zn[CF3SO3]2} [27-31]
to enable even zinc deposition by adjusting the adsorption of zinc ions on the anode surface or enabling the
formation of an _in-situ_ transition protection layer on the Zn anode surface. This layer provides a shielding
effect to suppress the dendrite growth [32] ; (iii) create a nanostructured current collector (e.g _.,_ 3D porous
copper skeleton, 3D flexible carbon nanotubes, or Ti3C2Tx MXene paper) as the zinc host to promote
uniform zinc deposition on the anode surface and effectively equalize the surface electric field [18,33-35] . Among
these strategies, modifying the Zn anode with a protective layer is straightforward and more effective.
However, most of current surface coating optimization methods focus on designing mechanically protective
film to block the dendrite growth. Herein, we propose a multifunctional zinc anode protection strategy that
considers mechanical strength, electrode surface compatibility, and overall stability.

This coating layer is constructed by a facile and low-cost approach. The buffer layer is formed on the surface
of zinc _via_ a strong cross-link reaction with lithium polysilicate (LSO) that features strong adhesion and
high corrosion resistance. As illustrated in Figure 1, zinc dendrites can be effectively suppressed by this
robust coating, leading to a long cycling life with low overpotential for the symmetric cells. Combining the
LSO/Zn anode with a MnO2 cathode, we achieved superior battery capacity at different currents from low to
high. Cycling stability is significantly improved for the Zn/LSO-MnO2 battery. The entire process is simple

Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51 Page 3 of 12

Figure 1. Schematic illustration of the comparison before and after LSO modification. LSO: Lithium polysilicate.

and efficient, offering an economic approach to fabricating dendrite-free zinc anodes.

## EXPERIMENTAL

Preparation of Zn-LSO anode
The initial substrates were made of pure Zinc foil of 10 µm thickness and cut into round disks 12.7 mm in
diameter. Then, the bare Zinc disks were coated with 150 µL LSO solution (Li2Si5O11, Sigma-Aldrich, Inc.) at
varying concentrations (0.5 _wt_ %, 1 _wt_ % and 1.5 _wt_ %). The coated disks were dried overnight to allow full
cross-link. The coated substrates were denoted as Zn-LSO-x, where x represented the concentration of LSO.

Preparation of α -MnO2 cathode
First, 0.0304 g Manganese sulfate monohydrate (MnSO4 · H2O, Fisher Scientific Inc.) was dispersed into 60
mL deionized (DI) water, and then 10 mL 0.5 M sulfuric acid (H2SO4, Fisher Scientific Inc.) was added
under vigorous stirring. After 20 min, 20 mL potassium permanganate (0.1 M, KMnO4) was added to the
solution, followed by 1-h ultrasonication. The mixture was then transferred into a 100 mL
polytetrafluoroethylene (PTFE) lined autoclave and reacted at 120 °C for 12 h. Afterward, the sediment was
separated using a centrifuge and washed with DI water till the pH reached 7. The resulting product was
collected, dried overnight at 60 in an oven, and denoted as α-MnO2.

Materials characterizations
The morphologies and structures of the anode and cathode materials were characterized using a scanning
electron microscope (SEM) (6610LV, JEOL, Japan) equipped with energy dispersive spectroscopy (EDS).
An _in-situ_ optical cell was used to construct symmetric cells with pure Zn and Zn-LSO-1 anodes for
monitoring the Zn plating process using an optical microscope (Nikon microscope). X-ray photoelectron
spectroscopy (XPS) analysis was conducted on an SSX-100 system (Surface Science Laboratories, Inc.)
equipped with a monochromated Al Kα X-ray source. The crystal structure of the samples was examined by
X-ray diffraction (XRD) (Rigaku Smartlab, Rigaku Americas, Inc. United States).

Assembly of symmetric cells and MnO2-based full cells
The symmetric cells consisted of two electrodes of Zinc or Zn-LSO-x, a piece of glass fiber separator, and
150 µL 2 M zinc sulfate (ZnSO4) electrolyte, assembled into CR2025 coin-type-cells. These cells were cycled
at various current densities of 0.5, 1, 3 and 5 mA cm -2 at a fixed specific capacity of 0.1 mAh cm -2 .

Page 4 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

The MnO2-based full cells were assembled using Zinc or Zn-LSO-x as an anode and MnO2 as a cathode. The
cathode was prepared by mixing MnO2, acetylene black and Polyvinylidene fluoride (PVDF) with a mass
ratio of 7:2:1, using N-Methyl-2-pyrrolidone (NMP, Fisher Scientific Inc.) as a solvent. The resulting slurry
was applied onto stainless-steel foil using a film applicator, and then dried at 120 °C in a vacuum oven for
24 h to remove excess solvent. The mass loading and thickness of the coated electrode materials were
1 mg cm -2 and 10 µm, respectively.

The Zn/MnO2 and Zn-LSO-x/MnO2 cells (bare Zinc or Zn-LSO-x anode and MnO2 cathode) were
assembled in the same procedure of the symmetric cells, but using 2 M ZnSO4 + 0.2 M MnSO4 as
electrolyte. All batteries were set for four hours before the electrochemical measurements.

Electrochemical characterization
The electrochemical measurements, including cyclic voltammetry (CV), linear polarization and
electrochemical impedance spectroscopy (EIS), were conducted on a potentiostat (PGSTAT128N,
Metrohm) for both symmetric and full cells. Galvanostatic charge/discharge measurements were conducted
using a Neware battery tester (BTS series, NEWARE, China).

## RESULTS AND DISCUSSION

Surface modification of zinc anode is critical for improving the cycle stability and capacity retention of zincion batteries. In pursuit of a high-performance zinc-ion battery, we engineered a zinc silicate coating layer
with mechanical and chemical stability on the surface of zinc anodes. The zinc silicate polymer protection
layer was formed _via_ the following steps: (i) The initial curing reaction involves concentrating the silicate/
[zinc film by evaporating the solvent, water (reaction Supplementary S1); (ii) Insolubilization occurs as the](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
[silicate matrix forms with zinc ions from the surface of zinc foil (reaction Supplementary S2); (iii) Further](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
hydrolysis of silicate in the presence of carbonic acid formed from atmospheric CO2 dissolved in water
[(reaction Supplementary S3); (iv) Production of polysilicic acid (reaction Supplementary S4), which then](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
reacts with zinc ions to form a zinc silicate polymer with a 3D structure (inorganic matrix, reaction
[Supplementary S5). The resulting zinc silicate polymer exhibits excellent mechanical strength due to the](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
strong combination of -Zn-O-Si-O-Zn- bonds. SEM was used to examine the surface morphologies of bare
zinc and LSO-coated Zn (LSO-0.5, LSO-1 and LSO-1.5). The bare zinc had a smooth surface with texture

[Figure 2A], while a rough surface with random pores was observed in Zn-LSO-1 [Figure 2B], and
[incomplete coating was observed for both Zn-LSO-0.5 and Zn-LSO-1.5 [Supplementary Figure 1]. In the](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
cross-sectional SEM images [Figure 2C and D], a coating layer with a thickness of ~2 _µ_ m could be clearly
observed for Zn-LSO-1, in contrast to the 10 _µ_ m thick bare zinc and irregular coatings for Zn-LSO-0.5 and
[Zn-LSO-1.5 [Supplementary Figure 1C and F]. In addition, the coating layer of Zn-LSO-1 was recognized in](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
[the element mapping, revealing a uniform distribution of Zn, O and Si [Supplementary Figure 2]. The](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
wettability of the electrolyte (2 M ZnSO4) on the surface of bare zinc foil and Zn-LSO-1 was assessed using
contact angle measurements. As depicted in Figure 2E and F, the Zn-LSO-1 electrode showed much better
wettability to electrolyte with a significantly reduced contact angle of 51.1° compared to 107.7° for bare zinc,
suggesting the significantly enhanced hydrophilicity/wettability of electrolyte on the electrode surface. The
enhanced hydrophilicity not only favors the electrolyte penetration and ion transports to the interfaces but
also enables reduced interfacial free energy between the electrode and electrolyte, and consequently leads to
homogeneous Zn plating and nucleation with low charge transfer resistance during the Zn stripping/plating
process [36,37] . Among the Zn-LSO-0.5, Zn-LSO-1 and Zn-LSO-1.5, the coating layer of Zn-LSO-1 was
believed to be most effective in suppressing dendrites due to its mechanical strength and the micropores
that offer smooth channels for zinc ion transportation.

Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51 Page 5 of 12

Figure 2. SEM images of (A) bare zinc; (B) Zn-LSO-1; and cross-sectional images of (C) bare zinc and (D) Zn-LSO-1; Contact angle for
the (E) bare Zn and (F) Zn-LSO-1 with 2 M ZnSO4 electrolyte. SEM: Scanning electron microscope; LSO: Lithium polysilicate.

To examine the stability of the modified zinc in electrolyte, both bare zinc and Zn-LSO foil were soaked in 2
M ZnSO4 electrolyte. As illustrated in Figure 3A, the bare zinc surface was severely corroded and became
thinner and fragile with an obvious color change to dark gray, indicating side reactions happened and
damaged the zinc foil. In contrast, the Zn-LSO surface showed no significant difference and the entire piece
retained its integrity even after bending, indicating a limited corrosion occurred. Furthermore, linear
polarization was conducted to investigate the corrosion resistance of the zinc foil before and after LSO
modification. Corrosion resistance can be indexed by two criteria: corrosion potential ( _Ecorr._ ) and corrosion
current density ( _jcorr._ ). Small _jcorr_ and/or large positive _Ecorr._ values are indications of superior corrosion
[resistance. As depicted in Figure 3B and Supplementary Figure 3, the LSO-modified zinc foils generally](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
showed a lower _jcorr_ and more positive _Ecorr._ than that of the bare zinc. The specific values are summarized in
Table 1, showing that the Zn-LSO-1 had the lowest _jcorr_ . (1.53 × 10 -6 A cm -2 ) and most positive _Ecorr._ (-0.973 V
_vs._ Ag/AgCl) in comparison with 1.53 × 10 -6 A cm -2 and -0.991 V for bare zinc, indicating that the LSO
coating could effectively improve the overpotential of HER and subsequently improve the corrosion
resistance in ZnSO4 electrolyte because of its electrochemical inertness. Interestingly, Zn-LSO-1 exhibited
the smallest charge transfer resistance among all prepared electrodes [Figure 3C and
[Supplementary Figure 4], demonstrating fast charge transfer with stable Zn plating/stripping kinetics.](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)

To investigate the suppression of dendrite growth during zinc plating/stripping process, a cell with a quartz
window for _in-situ_ optical microscopic monitoring was assembled and integrated into an electrochemical
working station. A high current density of 5 mA cm -2 with an areal capacity of 0.1 mAh cm -2 was applied to
Zn/Zn and Zn-LSO-1/Zn-LSO-1 symmetrical cells under charge/discharge cycling up to 60 min, with
optical images being recorded at 20 min intervals [Figure 4A and B]. It is worth noting that the bare zinc
electrode surface is always uneven at microscale, and the sharp points become preferential nucleation sites
of zinc dendrite. The zinc surface remained in its initial state for about 20 minutes. Then, corrosion near the
edge and plenty of nuclei on the Zn surface were observed. The corrosion became severe and large dendrites
evolved from the nuclei after ~ 60 min. In contrast, no obvious corrosion or dendrite growth was observed
on the surface of Zn-LSO-1 during the entire process (Note: the dark round spots are the signs of corrosion
for the uncoated zinc/bare zinc on the top flat area of the cell). Meanwhile, a lower and more stable voltage
hysteresis was observed for Zn-LSO-1 during the real-time recording in comparison with the fluctuated
profiles for the bare zinc electrode [Figure 4C]. The results confirmed the superior anti-corrosion and
dendrite-suppression performance of Zn-LSO-1.

Page 6 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

Table 1. A summary of corrosion current density ( _jcorr.)_ and potential ( _Ecorr._ ) of Zn, Zn-LSO-0.5, Zn-LSO-1 and Zn-LSO-1.5 anodes

Entry _jcorr._ (A cm

-2) _Ecorr._ (V _vs._ Ag/AgCl)

Zn 6.1 × 10-4 -0.991

Zn-LSO-0.5 4.08 × 10-4 -0.991

Zn-LSO-1 1.53 × 10-6 -0.973

Zn-LSO-1.5 4.23 × 10-4 -0.997

LSO: Lithium polysilicate; _Ecorr._ : Corrosion potential; _jcorr._ : Corrosion current density.

Figure 3. (A) Digital images of bare zinc and Zn-LSO-1 before and after being soaked in 2 M ZnSO4 for 16 days; (B) Tafel curves of Zn
and Zn-LSO-1 anode; (C) Nyquist plots of Zn and Zn-LSO-1 anode. LSO: Lithium polysilicate.

Figure 4. _In-situ_ optical microscope photos of the interface between electrolyte and electrode for symmetrical cells (A) Zn and (B) ZnLSO-1, during zinc plating/stripping process at a current density of 5 mA cm-2 with an areal capacity of 0.1 mAh cm-2; (C) The real time

voltage profiles of symmetrical Zn and Zn-LSO-1 cells. LSO: Lithium polysilicate.

The XPS was conducted to further understand the interface combination between Zn substrate and LSO for
Zn-LSO-1. Elements of Zn, Si, and O were all detected in the survey spectra which was consistent with the
composition of the formed zinc silicate polymer [Figure 5A]. Figure 5B showed that the high-resolution
spectra of Si 2p were deconvoluted into two main peaks. The one located at 102.7 eV was associated with

Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51 Page 7 of 12

Figure 5. (A) XPS spectra of Zn-LSO-1; The high-resolution XPS spectra of (B) Zn 2p; (C) Si 2p and O 1s regions of Zn-LSO-1. LSO:
Lithium polysilicate; XPS: X-ray photoelectron spectroscopy.

the Si-O-Zn bond, while the other one located at 103.9 eV was attributed to Si-O-Si [38] . Furthermore, the O
1s spectra were deconvoluted into three peaks with binding energies of 531.3, 532.4 and 533.6 eV

[Figure 5C], corresponding to Si-OH, Si-O-Si, and Si-O-Zn species, respectively [38,39], aligning with the
analysis of Si 2p spectra. Summarizing the aforementioned XPS analysis, it is strongly confirmed the
bonding status between LSO and Zn substrate is due to the formation of zinc silicate polymer coating layers.

Symmetrical cells using bare zinc, Zn-LSO-0.5, Zn-LSO-1 and Zn-LSO-1.5 anodes were prepared to test the
stability of Zn stripping/plating behaviors. The cells were charged/discharged at different current densities
with a fixed areal capacity of 0.1 mAh cm -2 . In comparison with the bare zinc electrode, the Zn-LSO-x
electrode exhibited much smaller voltage hysteresis and longer cycling life. Specifically, the Zn-LSO-1/ZnLSO-1 batteries were cycled for 835, 455 and 260 h at current densities of 0.5, 1 and 5 mA cm -2, respectively

[Figure 6A, B and C] which is significantly longer than that of Zn/Zn batteries (150, 148, and 50 h at current
densities of 0.5, 1 and 5 mA cm -2, respectively). In addition, smaller voltage hysteresis values of 66, 80 and
141 mV were observed for Zn-LSO-1/Zn-LSO-1 batteries compared with 159, 168, and 228 mV for bare Zn/
Zn batteries at current densities of 0.5, 1 and 3 mA cm -2, respectively [Figure 6D, E and F]. At a high current
density of 3 mA cm -2 [[Figure 6G and H, Supplementary Figure 5A-D], the symmetrical cells with Zn-LSO-1](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
electrodes exhibited the lowest overpotential of 118 mV and a stable cycling life of up to 344 h, compared to
261 mV and 110 h for the bare zinc electrode. The superior cycling stability of the symmetrical cells with
Zn-LSO-1 was also demonstrated at different current densities of 0.5, 1 and 5 mA cm -2 . The cycling of
Zn/Zn batteries under all current densities exhibited a sudden increase in voltage oscillation, indicating the
separator was pierced by zinc dendrites. In contrast, stable voltage hysteresis with negligible change in the
voltage oscillation amplitude was observed for Zn-LSO-1/Zn-LSO-1 batteries before failure, indicating
reversible Zn plating/stripping behaviors for Zn-LSO-1 electrode. It is worth noting that both the voltage
hysteresis and cycling life of Zn-LSO-1 electrodes were superior to the previously reported anodes for zinc[ion batteries [Supplementary Table 1]. Therefore, Zn-LSO-1 was promising for achieving a low](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
overpotential and ultralong lifetime due to its effective suppression of zinc dendrites.

As a demonstration for the real application of the Zn-LSO-1 anode, a full cell with an _α_ -MnO2 cathode was
[assembled using a CR3025 cell. The SEM images of the MnO2 are shown in Figure 7A and Supplementary](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
[Figure 6A, revealing an urchin-like nanostructure with abundant nanowires. XRD was conducted to](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
[identify the crystal structure of the MnO2. As shown in Supplementary Figure 6B, the characteristic peaks](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
located at 12.7°, 18.1°, 28.8°, 37.5°, 42.1°, 49.9°, 56.2°, and 60.3° corresponded to (110), (200), (310), (211),
(301), (411), (600), and (521) planes, respectively. The peaks match well with the standard diffraction
patterns of _α_ -MnO2 (JCPDS# 44-0141).

Page 8 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

Figure 6. Galvanostatic cycling stability and corresponding voltage profiles of symmetrical Zn and Zn-LSO-1 cells at various current
densities: (A, D) 0.5, (B, E) 1, (G, H) 3 and (C, F) 5 mA cm-2, with an areal capacity of 0.1 mAh cm-2. LSO: Lithium polysilicate.

-2, with an areal capacity of 0.1 mAh cm

-2. LSO: Lithium polysilicate.

For the electrochemical measurements, CV tests were performed at a scanning rate of 2 mV s -1 with a
voltage range of 0.8 - 1.9 V for both Zn/MnO2 and Zn-LSO-1/MnO2 cells. Two characteristic peaks were
observed around ~ 1.3 and 1.2 V in the cathodic sweep, which originated from the two-step reduction from
Mn 4+ to Mn 3+ and then to Mn 2+[25] . An anodic peak appeared at ~ 1.65 V during the anodic sweep, which can
be attributed to the reverse oxidation reaction [25] . Compared to the Zn/MnO2 battery, the Zn-LSO-1/MnO2
battery possessed a slightly enhanced current density and the anodic/cathodic peaks shifted to more
negative/positive voltages, respectively. A smaller voltage difference between the pair of cathodic/anodic
peaks for the MnO2 and Zn-LSO-1 electrodes was more conducive to Zn storage/delivery than the Zn
electrode [40-42] . These redox peaks were consistent with the plateaus observed in the galvanostatic charge/
discharge profiles of both Zn/MnO2 and Zn-LSO-1/MnO2 batteries [Figure 7B]. Overall, the charge/
discharge voltage profiles were similar. However, the Zn-LSO-1/MnO2 battery had a lower charge plateau
and higher discharge plateau than the Zn/MnO2 battery. These results indicated a reduced voltage gap and
polarization of the Zn-LSO-1/MnO2 battery due to the improved kinetics of Zn deposition and dissolution
on the anode. At a constant charge/discharge current density of 0.2 A g -1, the Zn-LSO-1/MnO2 battery

Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51 Page 9 of 12

Figure 7. (A) SEM image of MnO2; (B) CV curves of Zn/MnO2 and Zn-LSO-1/MnO2 cells at a scanning rate of 0.2 mV s-1; (C)

galvanostatic charge and discharge potential profiles and (D) cycling stability performance of Zn/MnO2 and Zn-LSO-1/MnO2 cells at a
current density of 1 A g-1. LSO: Lithium polysilicate; SEM: Scanning electron microscope; CV: Cyclic voltammetry.

Figure 7. (A) SEM image of MnO2; (B) CV curves of Zn/MnO2 and Zn-LSO-1/MnO2 cells at a scanning rate of 0.2 mV s

-1. LSO: Lithium polysilicate; SEM: Scanning electron microscope; CV: Cyclic voltammetry.

delivered a discharge capacity of 234 mAh g -1, significantly higher than the Zn-LSO-1/MnO2 battery (198
mAh g -1 ). Galvanostatic charge/discharge cycles at different current densities (0.2, 0.5, 1, and 1 A g -1 ) further
confirmed that the Zn-LSO-1/MnO2 batteries consistently outperformed the Zn/MnO2 battery in discharge
[capacity [Supplementary Figure 7A and B]. In Figure 7C, the galvanostatic discharge-charge (GDC) profile](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
at the current density of 0.2 A g -1 for the first cycle was presented, revealing discharge/charge capacities of
234.5 and 197 for Zn/MnO2 and Zn-LSO-1/MnO2 batteries, respectively.

The long-term cycling performance of both Zn/MnO2 and Zn-LSO-1/MnO2 batteries was investigated at a
current density of 1 A g -1 [Figure 7D]. The Zn-LSO-1/MnO2 battery consistently exhibited higher capacity
than the Zn/MnO2 battery. The capacity of the Zn-LSO-1/MnO2 battery gradually increased from 181 mA
g -1 to 230 mA g -1 after approximately 60 cycles, and maintained a capacity of 176 mA g -1 after 300 cycles,
with a capacity retention of 97% and coulombic efficiency (CE) of ~ 98.7%. In contrast, the capacity of the
Zn/MnO2 battery significantly decreased from 200 mA g -1 to 100 mA g -1, resulting in a loss of ~ 50% after
300 cycles. In addition, a capacity variation was observed in the initial cycles for Zn-LSO-1, attributed to the
initial activation process driven by the bulk-nanocrystalline evolution [43-45] . Rate performance of Zn and ZnLSO-1-based full cells at various current densities ranging from 0.1 to 2 A g -1 was also studied

[[Supplementary Figure 8]. Overall, the Zn/MnO2 battery exhibited lower rate capacities and worse retention](https://oaepublishstorage.blob.core.windows.net/articlepdfpreview202501/4051-SupplementaryMaterials.pdf)
compared to the Zn-LSO-1/MnO2 battery. Especially the Zn-LSO-1/MnO2 battery delivered high capacities
of 240, 221, 175, and 104 mAh g -1, corresponding to the current densities of 0.2, 0.5, 1, and 2 A g -1,
respectively. These results highlighted the excellent electrochemical performance of the Zn-LSO-1 anode,
indicating its promising potential for practical applications.

Page 10 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

## CONCLUSION

A zinc silicate polymer coating formed _via_ effective cross-link reactions between LSO and zinc foil can
directly serve as an anode for aqueous zinc-ion batteries. With the optimum LSO concentration, the zinc
silicate polymer coating effectively suppressed dendrite growth and exhibited excellent anti-corrosion
performance, as evidenced by improved wettability to electrolyte, low _jcorr._ and positive going _Ecorr_ . Symmetric
cells with the Zn-LSO anode demonstrate excellent cycling performance, characterized by long lifetime and
low overpotential at a wide range of current densities compared with bare zinc anodes. Moreover, full cells
using Zn-LSO anodes coupled with MnO2 cathodes present outstanding capacity performance and cycling
stability. The Zn-LSO anode is economic and promising for practical Zn battery applications. This study
opens a promising approach to constructing dendrite-free anodes for other aqueous metal-ion batteries.

## DECLARATIONS

Authors’ contributions
Conception, and characterizations, and manuscript drafting: Wang, K.
Materials characterization: Baule, N.; Hardy A.
Review and editing: Jin, H.; Qiao, H.; Schuelkea, T.; Fan, Q. H.

Availability of data and materials
The data is available from the corresponding authors upon reasonable request.

Financial support and sponsorship
This work was financially supported by the National Science Foundation (#1724941 and #1917577) and
Fraunhofer USA, and National Natural Science Foundation of China (No. 22109085).

Conflicts of interest
All authors declared that there are no conflicts of interest.

Ethical approval and consent to participate
Not applicable.

Consent for publication
Not applicable.

## REFERENCES

1. Huang, Z.; Ren, J.; Zhang, W.; et al. Protecting the Li-metal Anode in a Li-O2 battery by using boric acid as an SEI-forming additive.
_Adv. Mater._ 2018, _30_ [, e1803270. DOI](https://dx.doi.org/10.1002/adma.201803270)

2. Chen, L.; Fan, X.; Ji, X.; Chen, J.; Hou, S.; Wang, C. High-energy Li metal battery with lithiated host. _Joule_ 2019, _3_ [, 732-44. DOI](https://dx.doi.org/10.1016/j.joule.2018.11.025)

3. Adil, M.; Sarkar, A.; Roy, A.; Panda, M. R.; Nagendra, A.; Mitra, S. Practical aqueous calcium-ion battery full-cells for future
stationary storage. _ACS. Appl. Mater. Inter._ 2020, _12_ [, 11489-503. DOI](https://dx.doi.org/10.1021/acsami.9b20129)

4. Janoschka, T.; Martin, N.; Hager, M. D.; Schubert, U. S. An aqueous redox-flow battery with high capacity and power: the
TEMPTMA/MV system. _Angew. Chem. Int. Ed. Engl._ 2016, _55_ [, 14427-30. DOI](https://dx.doi.org/10.1002/anie.201606472) [PubMed](http://www.ncbi.nlm.nih.gov/pubmed/27754587)

5. Pasta, M.; Wessells, C. D.; Huggins, R. A.; Cui, Y. A high-rate and long cycle life aqueous electrolyte battery for grid-scale energy
storage. _Nat. Commun._ 2012, _3_ [, 1149. DOI](https://dx.doi.org/10.1038/ncomms2139)

6. Gheytani, S.; Liang, Y.; Wu, F.; et al. An aqueous Ca-ion battery. _Adv. Sci._ 2017, _4_ [, 1700465. DOI](https://dx.doi.org/10.1002/advs.201700465)

7. Zeng, X.; Hao, J.; Wang, Z.; Mao, J.; Guo, Z. Recent progress and perspectives on aqueous Zn-based rechargeable batteries with mild
aqueous electrolytes. _Energy. Storage. Mater._ 2019, _20_ [, 410-37. DOI](https://dx.doi.org/10.1016/j.ensm.2019.04.022)

8. Verma, V.; Kumar, S.; Manalastas, W.; Satish, R.; Srinivasan, M. Progress in rechargeable aqueous zinc-and aluminum-ion battery

Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51 Page 11 of 12

electrodes: challenges and outlook. _Adv. Sustain. Syst._ 2019, _3_ [, 1800111. DOI](https://dx.doi.org/10.1002/adsu.201800111)

9. Jia, H.; Wang, Z.; Tawiah, B.; et al. Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries. _Nano. Energy._
2020, _70_ [, 104523. DOI](https://dx.doi.org/10.1016/j.nanoen.2020.104523)

10.   He, P.; Yan, M.; Zhang, G.; et al. Layered VS2 nanosheet-based aqueous Zn ion battery cathode. _Adv. Energy. Mater._ 2017, _7_,
[1601920. DOI](https://dx.doi.org/10.1002/aenm.201601920)

11.   He, B.; Man, P.; Zhang, Q.; et al. Conversion synthesis of self-standing potassium zinc hexacyanoferrate arrays as cathodes for highvoltage flexible aqueous rechargeable sodium-ion batteries. _Small_ 2019, _15_ [, e1905115. DOI](https://dx.doi.org/10.1002/smll.201905115)

12.   Zhang, N.; Dong, Y.; Jia, M.; et al. Rechargeable aqueous Zn-V2O5 battery with high energy density and long cycle life. _ACS. Energy._
_Lett._ 2018, _3_ [, 1366-72. DOI](https://dx.doi.org/10.1021/acsenergylett.8b00565)

13.   Chen, S.; Lan, R.; Humphreys, J.; Tao, S. Salt-concentrated acetate electrolytes for a high voltage aqueous Zn/MnO2 battery. _Energy._
_Storage. Mater._ 2020, _28_ [, 205-15. DOI](https://dx.doi.org/10.1016/j.ensm.2020.03.011)

14.   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_ [, 2001599. DOI](https://dx.doi.org/10.1002/aenm.202001599)

15.   Zhang, Q.; Luan, J.; Tang, Y.; Ji, X.; Wang, H. Interfacial design of dendrite-free zinc anodes for aqueous zinc-ion batteries. _Angew._
_Chem. Int. Ed._ 2020, _59_ [, 13180-91. DOI](https://dx.doi.org/10.1002/anie.202000162)

16.   Hong, Z.; Ahmad, Z.; Viswanathan, V. Design principles for dendrite suppression with porous polymer/aqueous solution hybrid
electrolyte for Zn metal anodes. _ACS. Energy. Lett._ 2020, _5_ [, 2466-74. DOI](https://dx.doi.org/10.1021/acsenergylett.0c01235)

17.   Lee, J.; Kim, R.; Kim, S.; et al. Dendrite-free Zn electrodeposition triggered by interatomic orbital hybridization of Zn and single
vacancy carbon defects for aqueous Zn-based flow batteries. _Energy. Environ. Sci._ 2020, _13_ [, 2839-48. DOI](https://dx.doi.org/10.1039/d0ee00723d)

18.   Zeng, Y.; Zhang, X.; Qin, R.; et al. Dendrite-free zinc deposition induced by multifunctional CNT frameworks for stable flexible Znion batteries. _Adv. Mater._ 2019, _31_ [, e1903675. DOI](https://dx.doi.org/10.1002/adma.201903675)

19.   An, G.; Hong, J.; Pak, S.; et al. 2D metal Zn nanostructure electrodes for high-performance Zn ion supercapacitorss. _Adv. Energy._
_Mater._ 2020, _10_ [, 1902981. DOI](https://dx.doi.org/10.1002/aenm.201902981)

20.   Liu, X.; Lu, Q.; Yang, A.; Qian, Y. High ionic conductive protection layer on Zn metal anode for enhanced aqueous zinc-ion batteries.
_Chinese. Chem. Lett._ 2023, _34_ [, 107703. DOI](https://dx.doi.org/10.1016/j.cclet.2022.07.046)

21.   Li, J.; Yin, X.; Duan, F.; et al. Pure amorphous and ultrathin phosphate layer with superior ionic conduction for zinc anode protection.
_ACS. Nano._ 2023, _17_ [, 20062-72. DOI](https://dx.doi.org/10.1021/acsnano.3c05640)

22.   Liang, P.; Yi, J.; Liu, X.; et al. Highly reversible Zn anode enabled by controllable formation of nucleation sites for Zn-based batteries.
_Adv. Funct. Mater._ 2020, _30_ [, 1908528. DOI](https://dx.doi.org/10.1002/adfm.201908528)

23.   Zhao, K.; Wang, C.; Yu, Y.; et al. Ultrathin surface coating enables stabilized zinc metal anode. _Adv. Mater. Inter._ 2018, _5_, 1800848.
[DOI](https://dx.doi.org/10.1002/admi.201800848)

24.   Deng, C.; Xie, X.; Han, J.; et al. A sieve-functional and uniform-porous kaolin layer toward stable zinc metal anode. _Adv. Funct._
_Mater._ 2020, _30_ [, 2000599. DOI](https://dx.doi.org/10.1002/adfm.202000599)

25.   Kang, L.; Cui, M.; Jiang, F.; et al. Nanoporous CaCO3 coatings enabled uniform Zn stripping/plating for long-life zinc rechargeable
aqueous batteries. _Adv. Energy. Mater._ 2018, _8_ [, 1801090. DOI](https://dx.doi.org/10.1002/aenm.201801090)

26.   Zhao, Z.; Zhao, J.; Hu, Z.; et al. Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightenerinspired interphase. _Energy. Environ. Sci._ 2019, _12_ [, 1938-49. DOI](https://dx.doi.org/10.1039/c9ee00596j)

27.   Xu, W.; Zhao, K.; Huo, W.; et al. Diethyl ether as self-healing electrolyte additive enabled long-life rechargeable aqueous zinc ion
batteries. _Nano. Energy._ 2019, _62_ [, 275-81. DOI](https://dx.doi.org/10.1016/j.nanoen.2019.05.042)

28.   Wang, F.; Borodin, O.; Gao, T.; et al. Highly reversible zinc metal anode for aqueous batteries. _Nat. Mater._ 2018, _17_ [, 543-9. DOI](https://dx.doi.org/10.1038/s41563-018-0063-z)

29.   Zhang, Q.; Luan, J.; Fu, L.; et al. 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_ [, 15841-7. DOI](https://dx.doi.org/10.1002/anie.201907830)

30.   Li, W.; Wang, K.; Zhou, M.; Zhan, H.; Cheng, S.; Jiang, K. Advanced low-cost, high-voltage, long-life aqueous hybrid sodium/zinc
batteries enabled by a dendrite-free zinc anode and concentrated electrolyte. _ACS. Appl. Mater. Inter._ 2018, _10_ [, 22059-66. DOI](https://dx.doi.org/10.1021/acsami.8b04085)

31.   Han, J.; Lee, J.; Lee, H.; et al. In-situ coating of metal fluoride/polymer bi-layer protection for dendrite-free, anti-corrosive Zn-metal
anode. _Chem. Eng. J._ 2024, _485_ [, 149881. DOI](https://dx.doi.org/10.1016/j.cej.2024.149881)

32.   Guo, X.; Zhang, Z.; Li, J.; et al. Alleviation of dendrite formation on zinc anodes via electrolyte additives. _ACS. Energy. Lett._ 2021, _6_,
[395-403. DOI](https://dx.doi.org/10.1021/acsenergylett.0c02371)

33.   Yin, Y.; Wang, S.; Zhang, Q.; et al. Endrite-free zinc deposition induced by tin-modified multifunctional 3D host for stable zinc-based
flow battery. _Adv. Mater._ 2020, _32_ [, e1906803. DOI](https://dx.doi.org/10.1002/adma.201906803)

34.   Tian, Y.; An, Y.; Wei, C.; et al. Flexible and free-standing Ti3C2Tx MXene@Zn paper for dendrite-free aqueous zinc metal batteries
and nonaqueous lithium metal batteries. _ACS. Nano._ 2019, _13_ [, 11676-85. DOI](https://dx.doi.org/10.1021/acsnano.9b05599)

35.   Ci, J.; Cao, C.; Kuga, S.; Shen, J.; Wu, M.; Huang, Y. Improved performance of microbial fuel cell using esterified corncob cellulose
nanofibers to fabricate air-cathode gas diffusion layer. _ACS. Sustainable. Chem. Eng._ 2017, _5_ [, 9614-8. DOI](https://dx.doi.org/10.1021/acssuschemeng.7b01970)

36.   Hao, J.; Li, X.; Zhang, S.; et al. Designing dendrite-free zinc anodes for advanced aqueous zinc batteries. _Adv. Funct. Mater._ 2020, _30_,
[2001263. DOI](https://dx.doi.org/10.1002/adfm.202001263)

37.   Guo, W.; Cong, Z.; Guo, Z.; et al. Dendrite-free Zn anode with dual channel 3D porous frameworks for rechargeable Zn batteries.
_Energy. Storage. Mater._ 2020, _30_ [, 104-12. DOI](https://dx.doi.org/10.1016/j.ensm.2020.04.038)

38.   Dong, G.; Tian, G.; Gong, L.; et al. Mesoporous zinc silicate composites derived from iron ore tailings for highly efficient dye

Page 12 of 12 Wang _et al. Energy Mater._ 2025, _5_, 500012 https://dx.doi.org/10.20517/energymater.2024.51

removal: structure and morphology evolution. _Micropor. Mesopor. Mater._ 2020, _305_ [, 110352. DOI](https://dx.doi.org/10.1016/j.micromeso.2020.110352)

39.   Zhang, Y.; Zhu, L.; Chen, L.; Liu, L.; Ye, G. Influence of magnesia on demoulding strength of colloidal silica-bonded castables. _Rev._
_Adv. Mater. Sci._ 2019, _58_ [, 32-7. DOI](https://dx.doi.org/10.1515/rams-2019-0008)

40.   Huang, J.; Tang, X.; Liu, K.; Fang, G.; He, Z.; Li, Z. Interfacial chemical binding and improved kinetics assisting stable aqueous ZnMnO2 batteries. _Mater. Today. Energy._ 2020, _17_ [, 100475. DOI](https://dx.doi.org/10.1016/j.mtener.2020.100475)

41.   Wang, S. B.; Ran, Q.; Yao, R. Q.; et al. Lamella-nanostructured eutectic zinc-aluminum alloys as reversible and dendrite-free anodes
for aqueous rechargeable batteries. _Nat. Commun._ 2020, _11_ [, 1634. DOI](https://dx.doi.org/10.1038/s41467-020-15478-4)

42.   Ming, J.; Guo, J.; Xia, C.; Wang, W.; Alshareef, H. N. Zinc-ion batteries: materials, mechanisms, and applications. _Mater. Sci. Eng. R._
_Rep._ 2019, _135_ [, 58-84. DOI](https://dx.doi.org/10.1016/j.mser.2018.10.002)

43.   Liu, M.; Zhao, Q.; Liu, H.; et al. Tuning phase evolution of β-MnO2 during microwave hydrothermal synthesis for high-performance
aqueous Zn ion battery. _Nano. Energy._ 2019, _64_ [, 103942. DOI](https://dx.doi.org/10.1016/j.nanoen.2019.103942)

44.   Zhao, Q.; Chen, X.; Wang, Z.; et al. Unravelling H+/Zn2+ synergistic intercalation in a novel phase of manganese oxide for highperformance aqueous rechargeable battery. _Small_ 2019, _15_ [, e1904545. DOI](https://dx.doi.org/10.1002/smll.201904545)

45.   Liao, Y.; Chen, H.; Yang, C.; et al. Unveiling performance evolution mechanisms of MnO2 polymorphs for durable aqueous zinc-ion
batteries. _Energy. Storage. Mater._ 2022, _44_ [, 508-16. DOI](https://dx.doi.org/10.1016/j.ensm.2021.10.039)

Zhao, Q.; Chen, X.; Wang, Z.; et al. Unravelling H

+/Zn

본문 출처 PDF: PDF 보기 · 다른 PDF는 위 [PDF 업로드]로 올릴 수 있습니다.

활용가능성

이력 0건

아직 편집 이력이 없습니다. 저장할 때마다 이전 내용이 여기에 백업됩니다.