Anti-dendrite separator interlayer enabling staged zinc deposition for enhanced cycling stability of aqueous zinc batteries

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Article https://doi.org/10.1038/s41467-024-55153-6
# Anti-dendrite separator interlayer enabling staged zinc deposition for enhanced cycling stability of aqueous zinc batteries

Received: 31 January 2024

Accepted: 3 December 2024

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Dun Wang 1,4, Sanlue Hu 2,4, Titi Li 1, Caiyun Chang 2, Senlin Li 1,2, Songde Guo 1,
Huan Li 1, Qingming Liu 3, Jinqiu Gong 3, Jun Zhou 3 & Cuiping Han 1,2

Aqueous zinc ion batteries exhibit great prospects due to their low cost and
high safety, while their lifespan is limited by severe dendritic growth problems.
Herein, we develop an anti-dendrite hot-pressing separator interlayer through
a mass-producible hot-pressing strategy, by spreading metal-organic framework (MOF) precursor on nonwoven matrix followed by a simple hot-pressing
process. The in situ modification of MOF crystals on fiber surface processes
abundant nitrogenous functional groups and high specific surface area
(190.8 m 2 g −1 ) with a strong attraction to Zn 2+ . These features contribute to a
staged deposition behavior to promote uniform nucleation at high concentrations and two-dimensional grain growth at low concentrations.
Consequently, Zn | |Zn symmetrical cells with hot-pressing separator interlayer demonstrate cycle lives of 3000 hours at 2 mA cm −2, 2 mAh cm −2 . Moreover, Zn | |I2 pouch batteries with hot-pressing separator interlayer realizes
840 cycles lifespan with a capacity retention of 90.9% and a final discharge
capacity of 110.6 mAh at 25 °C.

Aqueous zinc-ion batteries (AZIBs) are appealing options for largescale electrochemical energy storage due to the distinctive advantages
of zinc metal negative electrodes and aqueous electrolytes 1–3 . Zinc is a
high-abundance metal, as a negative electrode offers the advantages of
intrinsic safety, low redox potential (− 0.76 vs. SHE), and high theoretical and volumetric capacity (820 mAh g −1, 5585 mAh cm −3 ) 1,4,5 . Meanwhile, the aqueous electrolyte shows a lower price, higher ionic
conductivity, and faster reaction kinetics than organic electrolytes 6 .
Many solutions, such as innovative microstructure design have been
proven as effective ways to increase the positive electrode performance in the past few years 7 . However, the widespread application of
AZIBs is still hindered by the challenges including Zn dendrite formation and associated side reactions on negative electrode 8 . These issues
can lead to dendrite puncture, dead zinc (i.e., zinc metal regions that
are electronically disconnected from the current collector) spalling,
and hydrogen evolution during the operation of the batteries,

resulting in rapid short-circuit failures and a notable decrease in the
coulombic efficiency of the AZIBs 9 . To address these issues, extensive
efforts have been conducted on the zinc-negative electrodes in recent
years, focusing on various aspects such as surface modification 10–13,
electrolyte component designs 14–16, alternative zinc powder negative
electrodes 17–19, anode-free electrodes 20–22, rocking-chair negative
electrodes 23–25, and innovative structural designs 26–28 . Most of those
strategies concentrate on the optimization of zinc surface structure
and solid-electrolyte interface or changing the negative electrode
reaction from metal deposition to ion embedding. It is not negligible
that the separator, as an important component of batteries, also plays
a vital role in improving the electrochemical performance of AZIBs 29 .

As a typical example illustrated in Supplementary Fig. 1, the
mostly used glass fiber (GF) separator is observed to have severe
dendrite and dead zinc problems in the Zn | |Zn symmetry battery due
to its inhomogeneous voids and low mechanical strength 30,31 . Thus

1Faculty of Materials Science and Energy Engineering, Shenzhen University of Advanced Technology, Shenzhen, China. 2Institute of Technology for Carbon
Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, China. 3 Towngas Energy Academy, Shenzhen, China.
4These authors contributed equally: Dun Wang, Sanlue Hu. [e-mail: zhou.jun05@towngas.com.cn; cp.han@siat.ac.cn](mailto:zhou.jun05@towngas.com.cn)

Mix up and spread on matrix

Metal salts

Organic ligands

Fluxing agents

MOF crystals

Hot-pressing for 30 min, 200�

32 cm

Fig. 1 | Preparation of HTS. The product of the HTS is a one-step hot-press strategy and graphic of finished Zn-based HTS.

searching for new separator materials or modifying the traditional
separators to control the Zn deposition and improve the electrochemical properties of AZIBs are the two common strategies that have
been reported in the past few years 32 . For the strategy to search for new
separator materials, the reported materials mainly focus on polymers,
such as Zn 2+ substituted Nafion membrane 33, single-ion Zn 2+ -conducting nanocellulose membrane 34, mesoporous polypyrrole paper 35, and
3D long-range ordered polyacrylonitrile nanofiber 30,34 . These materials
tend to show high mechanical strength, anti-corrosion, and zincophilic/Zn-rich functional groups. By replacing the traditional GF
separators with them, it is favorable to achieve homogenization of the
electric field as well as the Zn interest channel, slow down active
material loss, and improve the cycle life of AZIBs.

The second strategy is the modification of the GF separator by
using functional supramolecules 36, MOF materials 29, or polymers 37,38 .
These modified separators also demonstrated superior affinity for zinc
ions, due to the introduction of a large number of zincophilic groups,
which could avoid the accumulation of zinc ions on the electrode
surface, thereby regulating Zn deposition and improving the performance of AZIBs. Although the aforementioned methods are effective
in the optimization of electrochemical performances for separators,
the corresponding production techniques are mainly hydrothermal
method 29,36 or immersion method 33 . The current fabrication techniques are time-consuming and complicated and suffer from the limited
size of hydrothermal autoclave, which is not conducive to large-scale
production. Moreover, the intrinsic mechanism of the regulation of
deposition behavior and nucleation process by the separator has not
been clarified clearly in the previous studies 9,39 . Therefore, it is
imperative to explore a more concise method for separator preparations accompanied by the mechanism elaboration for advancing the
research in AZIBs.

Herein, we propose a one-step hot press strategy to prepare a
functional separator interlayer, and mainly discuss the role of
separators to influence the nucleation process with a unique staged
behavior. This hot press method is to simply spreads all mixed raw
materials on a nonwoven matrix, followed by the hot-pressing for
30 min. Based on the hot-pressing procedure, Metal-Organic Framework (MOF) crystals can be in situ modified on the fiber surface of the
matrix membrane and preserve the original ion transport channels
without physical obstruction. With this feature, MOF crystals can be
introduced into the separator, distributed in a ~ 160 μm thick space as
a carrier of functional groups in virtue of the high specific surface area
of MOFs, making these functional groups contact with the electrolyte
extensively and playing a significant regulatory role. Leveraging the
high active surface area, nitrogen-containing functional groups of

MOFs, and thick loading, the hot-press separator (HTS) achieves
staged deposition behavior by dynamic concentration control.
Through this mechanism, HTS can facilitate the crystallization kinetics
to induce the (002)Zn orientation and significantly decrease the growth
of dendrite. As a result, Zn | |Zn symmetric cells utilizing the HTS
demonstrate a cycling life of 4900 h at 1 mA cm −2, 1 mAh cm −2, and
3000 h at 2 mA cm −2, 2 mAh cm −2 . In Zn | |Cu cells, they exhibit 1650
cycles at 1 mA cm −2, 1 mAh cm −2 . Moreover, the stability and high
capacity of full-cell batteries with HTS are verified through a 120 mAh
high loading capacity for 840 cycles in Zn | |I2 full pouch cells. This
solution process the feature of low-cost, high-speed, and mass-producible, aims to extend the cycling life of AZIBs for the large-scale
application.

Results
The preparation and physicochemical properties of the HTS
separator
The HTS is prepared as signaled in Fig. 1. Metal salt, organic ligand, and
fluxing agent are blended evenly and spread on the fiber separator
matrix. A 30-minute hot-press step is applied, during which the raw
materials are converted to MOF crystal grains that wrap around the
surface through an in situ coordination reaction. Through the hotpressing solution, it is feasible to load MOF crystals on a fiber
separator, which promotes the expansion of the production scale. To
illustrate the potential for large-scale production, a representative
wide-area HTS (32 cm × 28 cm) was also fabricated using the one-step
hot-press solution.

The scanning electron microscope (SEM) shows a tight bond
between MOF crystals and the fiber matrix on HTS (Fig. 2a, b). The pore
structure of the separator is unaltered by MOF crystals, homologous
with the surface morphology of untreated nonwoven (bare separator)
(Fig. 2d, e). Energy dispersive spectroscopy (EDS) elemental mapping
images (Fig. 2c, f and Supplementary Fig. 2a, c) and corresponding EDS
energy spectra (Supplementary Fig. 3a, c) were utilized to characterize
the elemental information of the HTS and bare separator. The results
demonstrate a uniform distribution of zinc on the HTS, confirming the
attachment of MOF crystals. To further investigate the structure of the
attached crystals, X-ray diffraction (XRD) patterns (Fig. 2g) were
obtained to compare the lattice plane between the HTS and commercial zeolitic imidazolate framework-8 (ZIF-8). The peaks were
divided into specific crystal planes 40, and the results revealed that the
crystalline phase in the HTS exhibited a consistent diffraction angle
but with a more uniform diffraction intensity, indicating that the MOF
crystals in the HTS possess diverse crystallographic orientations, efficiently reducing inhomogeneity across the separator fibers. Fourier

Fig. 2 | Characterization of HTS. a–f SEM image (a, b), and EDS mapping (c) of
HTS.SEM image (d, e), and EDS mapping (f) of the bare separator. g XRD patterns of
HTS, bare separator, and commercial ZIF-8. h FTIR spectrum of HTS, bare

transform infrared (FTIR) spectra demonstrated the bonding structure
of the HTS (Fig. 2h), and the results support that the HTS incorporates
identical fingerprint areas. Notably, a peak at 421.1 cm −1 is assigned to
the vibrations of the Zn−N bond 41 . Stronger peaks observed at wavenumbers of 1577.4 cm −1 are identified as C = N bond, while the peaks at
1016.4 cm −1 and 1400.4 cm −1 are indexed as C − N bond. Another peak
at 1134.9 cm −1 is attributed to imidazole rings 42,43 . This suggests that
HTS is rich in nitrogen-containing groups, which have potential as
adsorption sites of Zn 2+ . In addition, a Co-based hot-press separator
(Co-HTS) was also prepared to demonstrate the versatility of the hotpress method. From the EDS elemental mapping images (Supplementary Fig. 2b) and corresponding EDS energy spectra (Supplementary Fig. 3b), the Co-HTS shows a significant uniform distribution of
cobalt. The SEM images (Supplementary Fig. 4) and XRD patterns
(Supplementary Fig. 5) indicate that zeolitic imidazolate framework-67
(ZIF-67) crystal grains are attached to the surface of Co-HTS. The FTIR
spectrums also proved the same peak position as the Zn-based HTS
(Supplementary Fig. 6), attributed to the imidazole ring in their
structure. N2 absorption isotherms were employed to provide further
evidence for the existence of porous MOF materials, as shown in Fig. 2i
and Supplementary Fig. 7. The relevant result illustrated that Zn-based
HTS shows higher loading than that of Co-HTS, in good accordance
with XRD diffraction intensity. In addition, a comparison is made

separator, and commercial ZIF-8. i Specific surface area of HTS, Co-HTS, and bare
separator, obtained from N2 adsorption isotherms.

between the unit prices of HTS and the usually-used GF separator. As
shown in Supplementary Table 1 and Supplementary Fig. 8, the cost for
the unit price of HTS is only 138 CNY m −2, significantly lower than that
of a commercial GF separator (2275 CNY m −2 ), indicating that HTS
possesses a enough cheap feature to fit the low-cost AZIBs. On the
other side, as shown in Supplementary Table 2, the electrolyte
absorption ratio of HTS is 205.7%, lower than that of the GF separator
(745.0%). The limited electrolyte absorption ratio of HTS is attributed
to the physical property of a nonwoven matrix. To address this issue,
the interlayer structure (two pieces of HTS stacked on both sides of a
piece of GF) is introduced in the following tests.

Morphology evolution of the HTS separator/Zn negative
electrode interface
To analyze the effect of the HTS on the negative electrode, Zn | |Zn
symmetrical cells were assembled using the interlayer structure. In situ
optical observation was used to intuitively display the deposition of Zn
metal on the negative electrode. The battery combined with HTS
exhibits a uniform layered deposition in the cross-sectional morphology (Fig. 3a). Meanwhile, the SEM of the Zn negative electrode after 20
cycles at 5 mA cm −2, 5 mAh cm −2 (Fig. 3b) also shows the typical stacking shape of hexagonal grains, which is attributed to both the electrocrystalline orientation (ECO) of (002)Zn and the exposed crystal face

Fig. 3 | Morphology characterization of Zn negative electrode with HTS. a, c In
situ optical observation of Zn negative electrode after plating 0, 10, 30, 50 min at a
current density of 5 mA cm −2 using the HTS (a) and bare separator (c) at the temperature of 25 °C. b, d SEM images of Zn foil negative electrode after 20 cycles at
5 mA cm −2, 5 mAh cm −2 using the HTS (b) and bare GF (d) at the temperature of

(ECF) 44 of [002]Zn. In contrast, in the case of a blank separator, the Zn
negative electrode with bare GF only exhibits visible hemispherical and
inhomogeneous zinc particles in the in situ optical observation image
(Fig. 3c), and the corresponding SEM image also reveals a raised micro
surface on the Zn negative electrode (Fig. 3d).

The side reactions on the negative electrode were explored
through the Zn surface phase analysis and hydrogen evolution reaction (HER) test. As shown in Supplementary Fig. 9, after a long cycle
time of 200 h at 1 mA cm −2, 1 mAh cm −2, the surface compositions of Zn
with HTS exhibit significant differences compared with bare separator.
XRD peaks at 13.0 and 19.6 degrees appeared on the Zn with the bare
separator, attributed to the by-product of Znx(OTf)y(OH)(2x−y)45. In

contrast, the Zn interface remained pure Zn peaks after 200 h of
cycling when HTS was employed as the separator, indicating the ability
of HTS to inhibit side effects. More appealingly, it is found the intensity
ratio of (002)Zn/(101)Zn was up to 387.1% after cycling for 200 h, which
is significantly higher than that of bare separator (61.7%). This phenomenon demonstrates the continuous optimization effect of HTS
during long cycles. Furthermore, the linear sweep voltammetry (LSV)
test in a 1 M Na2SO4 electrolyte to evaluate the HER potential on the
negative electrode side, as shown in Supplementary Fig. 10. The Zn

25 °C. e X-CT equipment structure and principle schema. f, g X-CT result of Zn | |Zn
symmetrical batteries using the HTS (f) and bare separator (g) after 20 cycles at
5 mA cm −2, 5 mAh cm −2 and temperature of 25 °C: (i) front view of negative electrode 3D reconstruction, (ii) Side view of battery 3D reconstruction, (iii) Side X-CT
view of battery cross-section.

negative electrode with HTS exhibits a HER potential of - 1.839 V,
which is 13 mV lower than that of the bare separator (− 1.826 V). These
results confirm the inhibition of hydrogen evolution in the presence
of HTS.

In addition, X-ray computed tomography (X-CT) is utilized to
further examine the surface structure of the negative electrode
beneath the separator. The equipment structure and principle of X-CT
are illustrated in Fig. 3e, the X-ray is emitted from a radiation source,
penetrating the symmetrical battery samples. Graphic information is
recorded from various viewing angles by rotating the sample, and the
results are combined to generate a 3D reconstruction. Figure 3f, g
presents the 3D model image and the cross-sectional CT image of the
battery with HTS and bare separator, in which the transparent
separator enables a clear view of the continuous macro morphology of
the Zn electrode. The phenomena of the CT result reveal that the
battery with HTS demonstrated a notable inhibition of dendrite
growth, evident from the smooth surface of Zn foil and the absence of
dendrites within the separator region (Fig. 3f(i−iii)). Conversely, it is
clear to observe a significant expansion of dendrites, which implant
into the bare separator turning to “death zinc”, as indicated by the
connected and discrete white Shadow between the electrodes

(Fig. 3g(i−iii)). The full cross-sectional CT scanning and 3D model were
shown in Supplementary Movie 1 (with HTS) and Supplementary
Movie 2 (with bare separator).

Dynamic Zn 2+ concentration regulation process of the HTS
separator
To investigate the impact of HTS on the Zn deposition process, a
comprehensive set of mechanistic characterizations was conducted.
As shown in Fig. 4a, b, and Supplementary Fig. 11, FTIR spectra are
provided to examine the solvent structure near the interface of the
separator. The results indicate that the peak corresponding to Zn−N at
421.1 cm −1 is significantly enhanced when HTS is soaked in 2 M Zn(OTf)2
(Fig. 4a), indicating the strong affinity between C − N, C = N groups and
Zn 2+ . Moreover, the peak of electrolyte at 1634.4 cm −1, which is
recognized as O − H bending 46 . Clearly, this peak is significantly
reduced and redshifted to 1630.1 cm −1, which proves that water activity
is inhibited in the presence of HTS, which results in the inhibition of
side reactions and the HER process. In contrast, the bare separator
exhibits a blue shift to 1637.3 cm −1 . Equivalently, the peak at 3341.6 cm −1

(Supplementary Fig. 11), corresponding to O − H stretching 47, is prominently attenuated. Besides, to evidence the stability of HTS, the FTIR
spectra of HTS after cycling are provided as shown in Supplementary
Fig. 12. The spectra exhibit that the main peaks of HTS remain constant
in intensity during long-time cycling. The corresponding test in electrolytes is shown in Supplementary Fig. 13, which indicates that the
MOFs loaded on HTS are stable for a long time in the electrolyte
environment without dissolution and leaching.

The results for transference numbers of Zn 2+ ions (t(Zn 2+ )) are
shown in Fig. 4c and Supplementary Figs. 14−16 (the corresponding
digital are shown in Supplementary Table 3 and the calculation of
t(Zn 2+ ) is shown in Supplementary Note 1). In a 2 M Zn(OTf)2 electrolyte, the HTS demonstrates a t(Zn 2+ ) of 0.66, approaching the t(Zn 2+ ) of
GF (0.68) and higher than that of the bare separator (0.42). Regularly,
the t(Zn 2+ ) of the bare separator is found to increase following the
concentration (from 0.37 in 1 M electrolyte to 0.48 in 3 M ones),
showing a positive correlation. Thus, it is promoted that a highconcentration environment existed around the HTS, increasing its
t(Zn 2+ ). In addition, the HTS exhibits a buffer behavior in the CV curves
of Zn | |Cu, as shown in Fig. 4d, indicating a concentration state transition during deposition/stripping. Furthermore, exchange current
density is calculated by the Tafel plot (Fig. 4e) and potential-current
fitness (Fig. 4f), both of which confirmed a lower corrosion rate and ion
transfer velocity in the presence of HTS. Notably, a transition stage was
found over - 0.95 ~ − 0.90 mV in the Tafel plots of HTS, indicating a
unique deposition process. Inspired by this observation, LSV curves
were conducted under broad negative polarized conditions with different separators (Fig. 4g, h and Supplementary Fig. 17). The limiting
current (iL) of a linear area can explain the effect of current on
deposition behavior, as Zn negative electrode tends to develop
(002)Zn orientation under 0.1iL ~ 1.0iL28. In the presence of HTS, the

limiting current is substantially decreased from 109.9 mA cm −2 for the
bare separator to 14.3 mA cm −2 for HTS. This implies that within the
HTS system, its negative electrode deposition tends to the (002)Zn
orientation under current conditions of 1.43 ~ 14.3 mA cm −2 . The
unique deposition process can be more visually represented in the
potential-capacity curves, as shown in Fig. 4i and Supplementary
Fig. 18. We promote that the optimization effect of HTS on Zn
deposition is maintained under different currents. At high current, the
HC stage is shortened and mainly manifested as grain refinement, and
the LC stage corresponds to the formation of (002)Zn orientation.
Obviously, the potential-capacity curves of the bare separator
demonstrate much smaller difference values of potential between Zn
nucleation and deposition (ΔE) than that of the bare separator at the
same current density, and the ΔE values of the HTS and bare separator
at 1 ~ 5 mA cm −2 were summarized as shown in Supplementary Fig. S19.

Meanwhile, the specific deposition curves corresponding to the
unique deposition process were found in HTS, which is exhibited as a
“stage behavior”.

It is worth noting that recent reports have highlighted the significance of concentration in determining deposition morphology 48,49 .
Then the “stage behavior” in the HTS from the point of view of concentration and deposition reaction are studied detailedly. By considering the simplified reaction as Eq. (1), we can derive the currentpotential equation as Eq. (2) based on the kinetics of the electrode
reaction 50 :

O + e � "R ð1Þ

i = FAk 0 ½COe �αFðE�E0Þ - CRe ð1�αÞFðE�E0Þ - ð2Þ

where O stands for oxidation state, R is the corresponding reduction
product, CO, CR are the concentrations of oxide and reduction product,
k 0 is the standard rate constant. α is the transfer coefficient, A is the
area of reaction, F is the Faraday constant, E and E 0 are the electrode
potentials.

In the case of Zn negative electrodes, where the concentration of
the reduction product in the solid phase remains constant, CR is
counted as 1. Consequently, the relationship between oxide concentration, current, and potential can be expressed as Eq. (3):

-
ie α
CO = FAK 0 + 1 e FðE�E0Þ ð3Þ

This equation indicates a positive correlation between oxide
concentration and potential under constant current conditions. Thus,
it can be assumed that with HTS, the deposition process under low
current density can be divided into two stages: a high Zn 2+ concentration stage (HC) and a low Zn 2+ concentration stage (LC), as
depicted in Fig. 4i. As the current increases, the HC stage disappears
and is replaced by the long LC stage, which is attributed to the fast
depletion of Zn 2+ .

Furthermore, the shorter linear area of LSV curves in Fig. 4g can
also be understood through Eq. (2). When the overpotential (E − E0) is
small enough, the Eq. (2) can be approximately equivalent to Eq. (4) as
follows:

i = FAk 0 ½�αFCOðE � E 0 Þ �ð1 � αÞFCRðE � E 0 Þ� ð4Þ

This equation corresponds to the linear area in LSV curves,
attributed to enough Zn 2+ ions at the first low overpotential stage. In
linear area, the main rate control steps of reaction are surface area and
activation. With the increasing overpotential, the curves turn to the
nonlinear area and finally become the Tafel curve when the overpotential is high enough. The changes in the nonlinear area are
attributed to the consumption of concentration, leading to the
reconstruction of the equilibrium reaction. Thus, the iL could be a
parameter to measure the speed of concentration polarization construction. For HTS, the lower iL indicates a faster concentration
depletion rate and directly contributes to the creation of the LC stage.

As for how concentration affects the deposition process, this has
been concluded from crystallization thermodynamics as shown in Eq.
(5) 51 :

rcrit = 2vmσ ð5Þ

nejηj

where the rcrit is the critical nucleus radius, νm is the volume occupied
by one atom in the crystal, σ is the specific surface energy, n is the
electron transfer number, and η is the overpotential of the electrode.

Fig. 4 | Electrochemical characterization and theoretical simulation of Zn
negative electrode with HTS. a, b FTIR spectra of HTS and bare separator
immersed in 2 M Zn(OTf)2 electrolyte, dry HTS, and 2 M Zn(OTf)2 electrolyte. c The
Zn 2+ transference number of Zn | |Zn batteries with HTS and GF in 2 M Zn(OTf)2, and
with bare separator in 1, 2, 3 M Zn(OTf)2. d−f CV curves (d), Tafel plots (e), and
current-potential fitting line from rate performance tests (f) of Zn | |Cu battery with
HTS and bare separator. The insert in d is the enlarged part of the dashed box.

_i=i0F_ _tot_ _/2RT_

g, h LSV curves and linear regional analysis of HTS and bare separator without iR
corrected. i potential-capacity curves during Zn nucleation and deposition at the
current density of 1 ~ 5 mA cm −2 using Zn foil as the working and counter electrode,
Ag/AgCl electrode as the reference electrode, and without iR corrected.
j Theoretical calculated adsorption energies of Zn atom on PET, cellulose, and ZIF-8
surface. k Schematic diagram of Zn ion deposition mechanism in the HTS and bare
separator.

In the steady-state growth phase of a negative electrode, the
Nernst equation (Eq. (6)) is introduced with a quasi-static perspective
to derive Eq. (7):

E = E 0 + RT nF

RT nF ln C C O R

= E 0 - RT nF ln CO ð6Þ

2vmσF
rcrit =
eRTln CO

ð7Þ

process, the negative electrode with an HTS separator commands
exceptional long-term cycling stability. Zn | |Zn cells with HTS exhibit a
cycling life of 3000 h (Fig. 5a) at 2 mA cm −2, 2 mAh cm −2, and 4900 h at
1 mA cm −2, 1 mAh cm −2 (Supplementary Fig. 24). On the other hand,
Zn | |Cu cells, to decouple the Zn deposition/stripping behavior, are
utilized in Coulombic efficiency (CE) plots to demonstrate significant
optimization of the HTS separator for negative electrode reversibility,
achieving 1650 cycles and 98.7% average CE (Fig. 5b). Further examination of deposition/stripping profiles as shown in Fig. 5c, d reveals a
distinct stage that appears in both deposition and stripping processes,
corresponding to HC and LC stages with different concentrations of
nucleation and grain growth. At a higher current density, the HTS
exhibits a cycling life span of 850 h at 5 mA cm −2, 5 mAh cm −2 (Fig. 5e),
with an 8.5% depth of discharge (DOD), and a 4210 mAh cm −2 cumulative charge/discharge capacity. Rate performance tests were conducted at current densities of 1 ~ 20 mA cm −2 (Fig. 5f), where the HTS
possesses better reversibility through the concentration control
strategy employed by the HTS separator. Conversely, batteries with
bare separators were short-circuited at high current, attributed to the
uncontrolled dendrite growth.

Furthermore, the Zn | |I2 battery was utilized to assess the practical
application of the HTS separator in a full-cell battery, using active
carbon as the positive electrode current collector to adsorb iodine by
electrolytic deposition solution. Figure 6a illustrates the cycling performance of Zn | |I2 full coin-type cells. When the bare separator was
utilized, the cell exhibited soft short 52 at cycle 450 th and dead short
circuits at cycle 1200 th, due to the inhomogeneous deposition on the
negative electrode. In sharp contrast, the full-cell batteries with GF at
the middle and double HTS separator close to both the negative
electrode and positive electrode (marked as double HTS) exhibited an
extended lifespan of over 15000 cycles, which can be attributed to the
high stability of the negative electrode. Full cells with single HTS close
to the negative electrode and GF close to the positive electrode
(marked as single HTS) were tested to analyze the effect of HTS on the
I2 positive electrode, as shown in the local magnification plot in Supplementary Fig. 25. The 1000 cycles capacity retention ratios were
calculated as Supplementary Table 4, compare with the capacity at
100 th cycle after activation. The result shows that the double HTS
structure processes a significantly higher capacity retention ratio
(99.6%) than that of the single HTS (97.8%) and bare separator (96.7%),
which superior performance is attributed to the shuttle resistance
function of MOFs 53 . To evaluate the impact of overpotential on the
application level of batteries, the specific energy of the I2 positive
electrode is introduced to measure the consolidated energy efficiency
(EE), as Eq. (8):

where the R is universal gas constant, and T is the temperature under
the Kelvin scale.

Besides, the SEM results under lower current and capacity were
provided as shown in Supplementary Fig. 20, the deposition of Zn with
HTS tends to smaller crystal grain at 1 mA cm −2, 1 mAh cm −2 . As the
condition becomes 2 mA cm −2, 2 mAh cm −2, the crystals start to larger
and denser, approaching the prototype of (002)Zn crystal orientation.
To verify the quantified component of Zn orientation, the XRD pattern
of the Zn negative electrode (Supplementary Fig. 21) was analyzed
following the same treatment as the SEM sample. Notably, the XRD
pattern shows a significant enhancement in the peak intensity ratio of
(002)Zn to (101)Zn on the HTS. With the current and capacity turns
higher, the peakintensity of the HTS group alsoincreased (from 101.8%
to 145.3%) all higher than that of pure Zn (98.0%), consistent with the
SEM results. While on the bare separator, the intensity ratio decreased
to 75.2%, attributed to the uneven deposition of the Zn negative
electrode. These results are consistent with the previous conclusion,
indicating the long LC stage corresponds to the formation of (002)Zn
orientation.

Within this framework, the critical nucleus radius is negatively
correlated to the Zn 2+ concentration. Consequently, during the HC
stage, the Zn negative electrode tends to form smaller nuclei with a
lower critical nucleus radius and energy barrier. As the Zn 2+ concentration decreases, owing to the depletion of Zn 2+ and limited mass
transfer dynamics, the deposition process translates into the LC stage.
In this stage, a larger critical nucleation radius impedes the nucleation
process, prompting the transformation of the Zn nucleus into the
growth stage and characterized by 2D directional growth with (002)Zn
orientation. To further determine the low kinetics of Zn 2+ transport in
HTS, the adsorption energies of Zn ions by HTS and bare separator
were calculated using density functional theory (DFT) calculations.
Due to the complex composition of HTS and bare separator, their main
components are used for the modeling and calculation here. ZIF-8 is
the main representative component of HTS, while polyethylene terephthalate (PET) and cellulose are the two main representatives of the
bare separator. Based on these main components, the surface models
(Supplementary Figs. 22, 23, and Supplementary Data 1) were established to calculate the adsorption energies of Zn ions, and the results
are shown in Fig. 4j. It is evident the adsorption energy of Zn ion on the
surface of ZIF-8 surface (− 3.95 eV) is much larger than that on PET and
cellulose (− 0.26 eV and - 0.34 eV), which indicates that the HTS can
effectively block the transport of Zn 2+, thereby slowing down its
kinetics.

Combined with the above experimental and theoretical analyses,
we have proposed that this HTS separator exhibits a unique mechanism of dynamic concentration regulation, as depicted in Fig. 4k, which
promotes dominantly oriented growth to reduce the formation of
dendrites and dead zinc in AZIBs.

Long stability performance and high loading capacity
application
To evaluate the stability of the negative electrode, Zn | |Zn symmetric
cells and Zn | |Cu cells were employed to compare cycling performance
while eliminating the influence of the positive electrode. Benefiting
from the function of regulating the negative electrode deposition

UtIΔt ð8Þ

En =

UðtÞIdt =

where En is the charge/discharge energy, U(t) is the real-time voltage,
Ut is the records real-time voltage in tests, I is the real-time current, and
Δt is the interval of records in tests. The results of full-cell specific
energy and energy efficiency are shown in Supplementary Fig. 26. The
average EE of full-cell with HTS over the first 400 cycles is 84.4%, ~ 0.9%
lower than that of the full cell with a bare separator (85.3%). In the long
term (400 ~ 1200 cycles), the EE of full-cell with HTS is comparable to
that of the bare separator system. Notably, over the whole cycle test,
the total average EE of full-cell with HTS is 87.1%, indicating a high
reversibility of energy storage.

In addition, cells with the HTS demonstrated steady capacity
retention throughout the charge/discharge profiles, as depicted in
Fig. 6b, c. To verify the capacity retention and self-discharge problem,
Zn | |I2 cells were fully charged to 1.8 V and rested for 48 h, then fully
discharged to 0.3 V (The charged and discharged curves are shown in
Supplementary Fig. 27). The discharged capacity retention ratio of

## a

2 mA cm -2, 2 mAh cm -2 HTS Bare

(1) (2)

300

150

-150

-300

-450

-600

120

100

(3) (4)

300
150
0

(1) (2) (3) (4)

-150
-300
0 10 20

-150
-300
900 910 920

-150
-300
1800 1810 1820

-150
-300
2700 2710 2720

## b

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Time (h)
## c d

Zn||Cu

Average: 98.67%

100

90
0 400 800 1200 1600

Bare

cycle 1 th

cycle 20 th

cycle 50 th

cycle 100 th

0.0 0.2 0.4 0.6 0.8 1.0

Capacity (mAh cm -2 )

HTS

Cycle 1 st

Cycle 20 th

Cycle 50 th

Cycle 100 th

Cycle 600 th

500

400

300

200

100

-100

1 mA cm -2, 1 mAh cm -2

HTS
Bare

0
0 400 800 1200 1600

Cycle number
## e

400 5 mA cm -2

0.0 0.2 0.4 0.6 0.8 1.0

Capacity (mAh cm -2 )
## f

20
15 15
1 2 5 810 108 5 2 1

400

200

-200

-400

Capacity: 1 mAh cm -2

0 10 20 30 40 50 60

Time (h)

Unit: mA cm -2

HTS
Bare

500

400

300

200

100

-100

200

-200

HTS
Bare

200

-200

-400

-600

-800

1 mAh cm -2
0 10 20

5 mAh cm -2

Preactivating
for 5 cycles
1 mA cm -2

200

-200

130 140

0 100 200 300 400 500 600 700 800

Time (h)

Fig. 5 | Electrochemical performance of Zn | |Zn and Zn | |Cu cells with HTS.
a Zn | |Zn symmetric cell cycling performance with different separators at
2 mA cm −2, 2 mAh cm −2 and temperature of 25 °C. b Columbic efficiency Zn | |Cu
cells with different separators at 1 mA cm −2, 1 mAh cm −2 discharge capacity, 0.5 mV
charge cut-off voltage, and temperature of 25 °C. c, d Corresponding charge/

Zn | |I2 cell with HTS is 91.7%, higher than that of the cell with a bare
separator (89.8%). The electrochemical behavior with HTS and bare
separator from the CV plot in Fig. 6d, e remained similar without the
shift in peak position, suggesting that the HTS has no significant effect
on the reaction process of the I2 positive electrode. Analogously, the
HTS and bare separator also had identical rate performance from
Fig. 6f, g. Furthermore, a comparison of the cycling performance of
full-cell batteries is presented in Supplementary Fig. 28 (The actual
data is shown in Supplementary Table 5). These results demonstrate
that the HTS exhibits significant performance optimization after
15,000 cycles, surpassing previous reports on AZIBs with different
separators.

To evaluate the performance of the HTS under more challenging
conditions and larger-scale applications, pouch cells were assembled
as Fig. 6h, i, using a 5 cm × 5 cm Zn foil negative electrode and 5 cm ×

5 cm I2 positive electrode with a loading capacity of 120 mAh, resulting
in an areal capacity of 4.8 mAh cm −2 and current density of 5 mA cm −2,
was achieved over 840 cycles (Fig. 6i) and 98.0 Ah high cumulative
capacity. For larger capacity, stratified pouch cells were assembled
using overlapped 2 pieces of positive electrode and 3 pieces of negative electrode with a size of 5 cm × 5 cm achieving stable operation with
800 mAh total capacity at 800 mA current, demonstrating the application prospect feasibility of HTS for large-scale energy storage
(Supplementary Fig. 29).

discharge profiles of Zn | |Cu cells. e Zn | |Zn symmetric cell cycling performance
with different separators at 5 mA cm −2, 5 mAh cm −2, and a temperature of 25 °C.
f Rate performance of Zn | |Zn symmetric cells with different separator at
1 ~ 20 mA cm −2 and temperature of 25 °C.

Discussion
In summary, the hot-press solution is proposed as a versatile and costeffective strategy for in situ modification of separators with various
MOF materials to address dendrite-related issues in Zn negative electrodes. The HTS is turned to be modified by in situ MOF crystals on the
fiber surface and without the obstruction of the original pore structure. On the Zn negative electrode, particularly the region obscured by
the separator, dendrites, and dead zinc are effectively restrained by
the HTS. Furthermore, the mechanisms of the dynamic concentrationregulation process were characterized by involving the guidance of
homogeneous nucleation at high concentrations and the promotion of
two-dimensional crystal growth at low concentrations attributed to
interfacial high concentration and slow diffusion kinetic of HTS. Based
on the aforementioned characteristics, the HTS enables a high stability
of negative electrode accompanied with a long cycling life of
3000 hours at 2 mA cm −2, 2 mAh cm −2, 4900 h at 1 mA cm −2,
1 mAh cm −2 . For the Zn | |I2 full-cell battery, the HTS allowed for a long
cell life of 15000 cycles at 1 A g −1 . A 120 mAh Zn | |I2 pouch cell could
also realize 840 cycles life and 80 cycles with 800 mAh high capacity,
demonstrating the application prospect feasibility of HTS for largescale energy storage. Through this work, we anticipated that a more
efficient and in situ approach to separator modification with MOF
materials could provide useful insights into designing low-cost and
high-performance separators for AZIBs.

Fig. 6 | Electrochemical performance of Zn | |I2 batteries with HTS. a Cycling
performance of Zn | |I2 cells with double HTS and bare separator at the temperature
of 25 °C. b, c Charge-discharge profiles of Zn | |I2 cells with HTS and bare separator
at temperature of 25 °C. d, e CV curves at 0.5 ~ 5 mV s −1 of Zn | |I2 cell with HTS and

Methods
Preparation of Zn-based hot-press separator (HTS)
37.5 g zinc acetate anhydrous (99%, Shanghai Aladdin Biochemical
Technology Co., Ltd.), 47.6 g 2-methylimidazole (98%, Shanghai Aladdin Biochemical Technology Co., Ltd.), and 11.9 g polyethylene glycol
(average Mn 4000, Shanghai Aladdin Biochemical Technology Co.,
Ltd.) were weighted and put into the grinding jar. After mixing for
3 min on an SFM-7 vacuum mixer (Shenzhen Kejing Star Technology
Co., Ltd.) at a rotation speed of 320 rpm/min, the uniform mixture was
spread on a nonwoven fiber separator (LD-3, Sontara®), and pressed
under 200 °C for 30 min. Before use, the nonwoven fiber separator was
washed with ethanol (AR, Shanghai Lingfeng Chemical Reagent Co.,
Ltd.). Then the modified separator was washed in ethanol and deionized water to remove unreacted raw material and finally
dried at 60 °C.

Preparation of Co-based hot-press separator (Co-HTS)
37.5 g Co(OAc)2 (99%, Shanghai Aladdin Biochemical Technology
Co., Ltd.), 47.6 g 2-methylimidazole (98%, Shanghai Aladdin Biochemical Technology Co., Ltd.), and 11.9 g polyethylene glycol

bare separator at temperature of 25 °C without iR corrected. f, g Rate performance
of Zn | |I2 cell with HTS and bare separators at temperature of 25 °C. h, i Photograph
and cycling performance of Zn | |I2 pouch cells at temperature of 25 °C.

(average Mn 4000, Shanghai Aladdin Biochemical Technology Co.,
Ltd.) were weighted and put into grinding jar. After mixing of 3 min
on SFM-7 vacuum mixer (Shenzhen Kejing Star Technology Co., Ltd.)
at a rotation speed of 320 rpm/min, the uniform mixture was spread
on a nonwoven fiber separator (LD-3, Sontara®), and pressed under
200 °C for 30 minutes. Before use, the nonwoven fiber separator was
washed with ethanol (AR, Shanghai Lingfeng Chemical Reagent Co.,
Ltd.). Then the modified separator was washed in ethanol and deionized water to remove unreacted raw material and finally
dried at 60 °C.

Electrode and electrolyte preparation
Zinc trifluoromethanesulfonate (Zn(OTf)2, 98%, Shanghai Aladdin
Biochemical Technology Co., Ltd.) was dissolved in deionized water as
2 M Zn(OTf)2 solution for the electrolyte in all batteries. Zn foil
(100 μm, Wuhan Luojia Yanxin Technology Co., Ltd) was treated with a
metal polishing agent (Nihon Maryo Kogyo Co., Ltd.) and soaked in
ethanol, and sonicated for ten minutes as the negative electrode. Cu
foil was cleaned by ethanol as the positive electrode in Zn | |Cu cells.
Activated carbon (YP-50, Kuraray Co., Ltd), Ketjen black (Suzhou

Sinero Technology Co., Ltd), and poly(tetrafluoroethylene) (PTFE)
powder (Guangdong Canrd New Energy Technology Co., Ltd.) were
mixed with a mass ratio of 8:1:1, made from dry film by hot rolling
method, and loaded on titanium mesh (Hebei Mengshang Metal Mesh
Industry Co., Ltd) as a current collector of positive electrode. I2 on the
current collector was prepared by electrodeposition method with
0.5 M ZnSO4 and 1 M KI mixed solution as electrolyte and Zn foil as
counter electrode.

Electrochemical measurements
Zn | |Zn, Zn | |Cu, and Zn | |I2 cells were assembled in CR-2032 cointype cells (stainless steel, Guangdong Canrd New Energy Technology
Co., Ltd.), using HTS | GF | HTS or bare|GF|bare as separator with
160 ~ 200 μL electrolyte and ensure the separators were completely
wetted. The size of the spring is 15.4 × 1.1 mm. The GF is brought from
Whatman™ (1821−110). The cycling performance of negative electrode by galvanostatic charge/discharge tests, rate performance, and
Zn 2+ transference number was used Zn | |Zn coin cells with diameter
16 mm separator and 12 mm Zn foil. The electrochemical impedance
spectroscopy (EIS) was conducted in a potentio mode, and the frequency was between 200 MHz and 100 kHz, and the recording condition was 10 points per decade. Before each test, the cells were
rested for 30 min. The cyclic voltammetry (CV) curves (− 0.2 ~ 0.4 V)
and columbic efficiency of the negative electrode were tested in Zn | |
Cu coin cells with a diameter 16 mm separator, 12 mm Zn foil, and
16 mm Cu foil. The Tafel plots, linear sweep voltammetry (LSV) plots,
and potential-capacity curves during Zn nucleation and deposition
were tested in a beaker cell with Zn foil as the working and counter
electrode, Ag/AgCl electrode as the reference electrode (pre-soaked
in 3 M KCl for 12 h for calibration), with 15 mL electrolyte. HTS, or
bare separator was unfolded over the working electrode and secured
on the backside with double-sided tape. To exhibit the direct results,
iR-correction was not used in the 3-electrode cell test. Three tripartite electrode holes on the beaker cells were utilized to ensure the
position of electrodes was the same in each test. The active size of
working and counter electrodes was 1 × 1 cm. The cycling performance by galvanostatic charge/discharge tests, CV curves, and rate
performance were measured with round zinc foil negative electrode
(diameter: 12 mm) and square I2 positive electrode (1 cm × 1 cm), with
a controlled ~ 5 mg cm −2 I2 loading. Zn | |I2 full pouch cells were
assembled from 5 cm × 5 cm (or 8 cm × 8 cm) Zn foil negative electrode, 5 cm × 5 cm (or 8 cm × 8 cm) I2 positive electrode (~ 25 mg cm −2

I2 loading) with 80 ~ 120 μL cm −2 electrolyte and ensure the separators were completely wetted. For coin cells, the positive electrode
materials were loaded on a single face of titanium mesh close to the
separator, and for pouch cells, those were loaded on a double face of
titanium mesh for higher loading. All area-based current densities
were calculated by the area of the negative electrode, and specific
currents were calculated by the mass of iodine in the positive electrode. The cell assembling and electrochemical measurements were
conducted in an air-conditioned room at 25 ± 0.5 °C. The cycling
performance tests were carried out on the CT3002A LAND battery
testing system. The CV, LSV, and EIS curves were tested on a VSP-3e
multichannel electrochemical workstation.

Characterizations
X-ray Diffraction (XRD). X-ray diffraction measurements were conducted on a MiniFlex600 diffractometer fitted with Cu-Kα X-rays
(λ = 1.5406 Å) radiation at a scan rate of 10°/min. Commercial ZIF-8
powder (Shanghai Aladdin Biochemical Technology Co., Ltd.) and
commercial ZIF-67 (Nanjing XFNANO Materials Tech Co., Ltd) were
measured to compare crystal structure.

N2 adsorption isotherms. N2 adsorption isotherms were tested on a
MicrotracBEL BELSORP MINI X. For pretreatment, the separator

samples were cut into pieces smaller than 2 mm and vacuum degassed
for 12 h under 60 °C.

Scanning electron microscopy (SEM). The SEM measurements of
separators were obtained from Thermo Fisher Scientific Apreo 2 S
HiVac under the electron current of 13 pA and accelerating voltage of
2 kV to avoid the charged effect. The SEM results of the negative
electrode were through Phenom Pharos G2 Desktop SEM, under 5 kV
acceleration voltage. Negative electrodes after cycles were rinsed with
deionized water and ethanol. Then the negative electrodes were fast
air-drying at room temperature and carefully transferred into an SEM
device. The separator and negative electrode samples were stable in
the air and treated fast to protect their morphology.

In situ optical observation. The in situ optical image during the
deposition process was carried out by DPX M6000-3D Digital Microscope (Deltapix) with MicroElab R-2-CS-TC Optical-electrochemical
test cell (Cross-section). To demonstrate the morphology of the sample at a certain depth, an ultra-deep field image was formed from
different depths.

X-ray Computed tomography (X-CT). The X-CT was measured by a
Phoenix V|tome|x M300 under an accelerating voltage of 140 kV, a
current of 180 μA with a resolution of 3 μm, and an exposure time of
334 ms. The 3D reconstruction model and cross CT-view were carried
out by integrating the results of scans from different angles.

Fourier transform infrared (FTIR). The FTIR spectrums were carried
out through an Invenio S FT-IR Spectrometer at reflex mode in the
wavenumber range of 400 ~ 4000 cm −1 . The separator results were
tested by directly pressing the separator against the viewing window.
The results of the percolate separator were carried out by dropping
enough electrolytes on the corresponding separator.

Computational methods. All the density functional theory (DFT)
calculations were conducted using the projector-augmented wave
(PAW) method within the Vienna Ab initio Simulation Package (VASP)
software 54 . The plane-wave cutoff energy of the geometry optimization and adsorption calculations was set to 500 eV. The generalized
gradient approximation (GGA) method, specifically the PerdewBurke-Ernzerhof (PBE) 55, was utilized as the exchange-correlation
function. In addition, the DFT-D3 (Grimme) 56 was employed to
account for the van der Waals interactions. The structure models of
PET, cellulose, and ZIF-8 were established based on their chemical
composition and previous literature 57 . In the calculations for
adsorption energy (Ea), slab models were constructed by using a
2 × 4 × 2 supercell for PET, a 4 × 3 × 2 supercell for cellulose, and a
1 × 1 × 1 conventional cell for ZIF-8, respectively. A 20 Å vacuum layer
was established along the z-direction of these models. The convergence criteria were set to 10 −4 eV for total energy and < 0.03 eV Å –1

for the force on each atom. Γ-only k-meshes were used for geometry
relaxation, allowing all atoms to relax. The Ea was defined as:

Ea = Eslab + Zn � Eslab � EZn

where Eslab+Zn represents the total energy of the slab model with an
adsorbed Zn atom, Eslab is the energy of the free slab model, and EZn is
the energy of a free Zn atom. Furthermore, the Ea calculations incorporated dipole corrections along the z-direction.

Data availability
The data that support the findings of this study are available within the
text, including the Methods, and Supplemental information. Raw
datasets related to the current work are available from the corresponding author upon request. Source data are provided in this paper.

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Acknowledgements
The work was financially supported by the National Natural Science
Foundation of China (22279160 awarded to C.H.), the Shenzhen Science
and Technology Program (RCYX20221008092934093 awarded to C.H.,
JCYJ20230807140902005 awarded to S.H.), and Towngas Energy

Academy. The computing work associated with this paper was supported by the public computing service platform provided by SIAT.

Author contributions
C.H. and J.Z. conceived the project. D.W., C.H., C.C., and S.L. designed
the experiments. D.W., T.L., S.G., H.L., Q.L., and J.G. synthesized the
materials. D.W., T.L., and S.L. did the materials characterizations. S.H. did
the theoretical simulations. All authors contributed to the data analysis
and discussions. S.H., D.W., and T.L. wrote the manuscript. C.H., J.Z.,
C.C., S.H., and D.W. revised the manuscript.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary information The online version contains
supplementary material available at
[https://doi.org/10.1038/s41467-024-55153-6.](https://doi.org/10.1038/s41467-024-55153-6)

Correspondence and requests for materials should be addressed to
Jun Zhou or Cuiping Han.

Peer review information Nature Communications thanks the anonymous, reviewers for their contribution to the peer review of this work. A
peer review file is available.

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