Research Article

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A Molecular-Sieve Electrolyte Membrane enables Separator-

Free Zinc Batteries with Ultralong Cycle Life
Junbo Zhu, Zhe Bie, Xinxin Cai, Zhaoyang Jiao, Ziting Wang, Jingchen Tao,
Weixing Song,* and Hong Jin Fan*

and electrolyte engineering.[5] Among

The poor stability of the zinc-metal anode is a main bottleneck for practical them, surface modification of Zn anode
application of aqueous zinc-ion batteries. Herein, a series of molecular sieves is an effective approach to reconstruct the
with various channel sizes are investigated as an electrolyte host to regulate electrolyte–anode interface. The reported
the ionic environment of Zn2+ on the surface of the zinc anode and to realize protective layers include inorganic metal
compounds such as ZnS,[6] ZnF2,[7]
separator-free batteries. Based on the ZSM-5 molecular sieve, a solid–liquid
CaCO3,[8], CuO,[9] and TiO2,[10] and organic
mixed electrolyte membrane is constructed to uniformize the transport of polymers like hydrogel,[11] polyamide,[12]
zinc ions and foster dendrite-free Zn deposition. Side reactions can also be and polyethylene oxide.[13] However, most
suppressed through tailoring the solvation sheath and restraining the activity coating layers increase the interfacial
of water molecules in electrolyte. A V2O5||ZSM-5||Zn full cell shows signifi- resistance and show low ionic conductivity.
The inorganic compound layers generally
cantly enhanced performance compared to cells using glass fiber separator.
show deficiency in elasticity and flexibility,
Specifically, it exhibits a high specific capacity of 300 mAh g−1, and a capacity which inevitably affect the stability of the
retention of 98.67% after 1000 cycles and 82.67% after 3000 cycles at 1 A g−1. protective layers and limit their functions
It is attested that zeolites (ZSM-5, H-β, and Bate) with channel sizes of 5–7 Å during long-term Zn plating/stripping.
result in best cycle stability. Given the low cost and recyclability of the ZSM Moreover, these protective layers cannot
and its potent function, this work may further lower the cost and boost the replace separators, and thus separators
are still needed as an indispensable part
industrial application of AZIBs.
of AZIBs. As the most frequently used
battery separator, glass fiber (GF) has high
durability and chemical inductance, but
1. Introduction it is expensive and hardly regulates metal-ion flux for lack of
the function of protective layers.[14] For example, while metal–
Aqueous zinc-ion batteries (AZIBs) are regarded as a promising organic frameworks have been used to regulate water activity
next-generation energy storage device due to the advantages of and ion flux,[15] the separator is still required, and the cells
the low-cost, nonflammable zinc metal, and the aqueous elec- exhibit low conductivity and high cost. To make AZIBs a viable
trolyte.[1] However, the practical application of AZIBs is hin- and competitive technology with respect to the dominating
dered by low coulombic efficiency (CE) and insufficient cycle lithium-ion batteries and lead-acid batteries, cutting the
life due to the Zn-metal instability, which is caused by reasons material cost while maintaining long-cycle performance is
including uncontrolled dendrite growth, hydrogen evolution, increasingly required.
and surface passivation (Figure 1a).[2] To mitigate these issues, Herein, a series of molecular sieves with different channel
various zinc anode protection strategies have been developed, sizes are introduced to construct solid–liquid mixed electro-
such as Zn-metal surface modification,[2e,3] 3D zinc structure,[4] lyte. The rational of design is that, the molecular sieves will
not only function as an effective separator, but also regulate the
solvent structure and Zn-ion transport. Thus, the molecular-
J. Zhu, Z. Bie, X. Cai, Z. Jiao, Z. Wang, J. Tao, W. Song sieves electrolyte membrane enables more stable and reversible
Beijing Key Laboratory for Optical Materials and Photonic Devices Zn deposition compared to conventional GF separator. A
Department of Chemistry molecular sieve is a crystalline aluminum silicate formed by
Capital Normal University
Beijing 100048, P. R. China an oxygen bridge between silica tetrahedron and alumina
E-mail: songwx@cnu.edu.cn tetrahedron.[16] Due to an intersecting and 3D channel system,
H. J. Fan these molecular-sieve electrolyte membranes with channel
School of Physical and Mathematical Sciences sizes of 0.3–2.5  nm are proven capable of uniformizing the
Nanyang Technological University zinc-ion flux and transport. The observed decrease in activity
Singapore 637371, Singapore
E-mail: fanhj@ntu.edu.sg
of free water and solvated water in electrolytes can minimize
the side reaction of zinc anodes and prolong the cycle life of
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202207209. AZIBs (Figure  1b). Based on this ZnSO4−ZSM-5 mixed elec-
trolyte, a V2O5||ZSM-5||Zn full cell without separator exhibits
DOI: 10.1002/adma.202207209 superior cycle stability at both low and high current densities.

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Figure 1.  ZSM-5 molecular sieve as solid–liquid hybrid electrolyte. a) Schematic illustration of typical reaction process (dendrite growth, hydrogen
evolution, corrosion, and passivation) of the bare Zn anode in ZnSO4 electrolyte. b) Regulating water activity using a ZSM-5 membrane. c) 3D channel
structure of ZSM-5. d) Scanning electron microscopy (SEM) images of the side view, and e) the top view of the ZSM-5 membrane. f) EDS mapping of
Si, O, Zn, and S element distribution. g) XPS of a ZSM-5 film before and after immersion in ZnSO4 solution. h,i) SEM images of Zn electrodes after
50 cycles in the GF electrolyte (h) and the ZSM-5-based electrolyte (i).

We establish that the molecular sieves (ZSM-5, H-β, and Bate)
with channel sizes of 5–7 Å can effectively reduce the water
activity in the electrolyte. Because of the ease and economy of
such solid–liquid mixed electrolyte membranes, this study may
provide a new solution for AZIBs for safe and durable energy
storage.
2. Results and Discussion
2.1. Fabrication of ZnSO4−ZSM-5 Mixed Electrolyte
Membrane and Half-Cell Performance
In this study, a tableted molecular-sieve membrane was
employed both as a mixed electrolyte and a separator for AZIBs.
The molecular-sieve membrane is immersed completely in 3 m
ZnSO4 solution (Figure S1, Supporting Information), allowing
the electrolyte to adequately enter molecular-sieve channels.
Limited space of these channels restricts the solvated water
around Zn2+ in the electrolyte. The ZSM-5 molecular sieve is
a kind of silicoaluminate with a simple structure that lacks a
cage structure found in other molecular sieves such as A-, X-,
and Y-type.[17] Its skeleton is made up of two types of vertical
cross channels: one is oval channel with a long axis of 5.7–5.8 Å
and a short axis of 5.1–5.2 Å (Figure  1c). The other is a “Z”
shaped channel with an aperture of 5.4 Å and a channel angle
of 110°. Systematic investigation presents the optimal thick-
ness of ZSM-5 film was 300  µm (Figure  1d), which is similar
to the thickness of the GF separators (310  µm) in coin cells.
The membrane with thinner thickness tends to break and has
a low ionic conductivity (Figure S2, Supporting Information),
whereas thicker membranes will lower the energy density of
the cell. The mass of ZSM-5 electrolyte membrane is less than
one third of GF electrolyte membrane (Figure S3, Supporting
Information), which reduces the amount of ZnSO4 electro-
lyte and will improve the special energy density of the battery.
Furthermore, the cost of the ZSM-5 is ≈l8% of that of the GF
separator in a cell, which is conducive to cost reduction. The
ZSM-5 molecular-sieve membrane has a flat surface and PVDF
binds the microcrystals well (Figure 1e). The energy-dispersive
X-ray spectro­scopy (EDS) mappings of the ZSM-5 electrolyte
membrane confirms the abundance of Si and O elements,
which provide sites for adsorbing water molecules (Figure  1f).
The uniform distribution of Zn and S elements in the elec-
trolyte membrane indicates that Zn ions successfully enter
the ZSM-5 molecular-sieve channels. The presence of ZnSO4

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Figure 2.  Comparison between ZnSO4 electrolyte with GF separator and ZnSO4−ZSM-5 mixed electrolyte without separator. a) Tafel plots. b) Electro-
chemical stability windows for hydrogen evolution measured by linear sweep voltammetry at 1 mV s−1 in Zn–Cu half cells. c) The Zn-ion transference
numbers (tZn2+). d) Long-term galvanostatic cycling performance of symmetric cells at 1 mA cm−2 and an areal capacity of 1 mA h cm−2. e) Coulombic
efficiencies of Zn–Cu half cells during cycles at 1 mA cm−2.

electrolyte in zeolite membrane is also supported by the X-ray
photoelectron spectra (XPS) (Figure  1g). To clarify the func-
tion of ZSM-5 membrane, the surface of the Zn anodes after
symmetric cells cycling is examined. For the GF separator,
the cycled Zn presents distinct lamellar porous dendrites
(Figure  1h) due to uneven zinc deposition. In contrast, the
anode using ZSM-5-based electrolyte retains a flat and dense
morphology (Figure 1i).
The effect of ZSM-5-based mixed electrolyte on corrosion-
resistant performance was evaluated by the linear polarization
measurements (Figure 2a). The corrosion current densities
(icorr) of ZnSO4−ZSM-5 electrolyte and ZnSO4 electrolyte are
1.3 and 9.3  mA cm−2, respectively. The reduced icorr indicates
stronger corrosion resistance and lower corrosion reaction
rate. Hydrogen evolution reaction (HER) is also significantly
suppressed as can be seen from the negligibly small HER cur-
rent compared to that in case of GF (Figure 2b). These results
imply the effective restriction effect on both free water in the
electrolyte and solvated water around Zn2+. Without the elec-
trolyte membrane, the local pH increase will result in side reac-
tion by-products such as Zn hydroxides and zincates which are
detrimental and hinder further deposition of Zn. In addition
to inhibiting HER, the ZSM-5-based electrolyte membrane is
also expected to facilitate the diffusion of Zn2+ toward uniform
striping and plating. This can be reflected by the transference
number of zinc ions (tZn2+) derived from the electrochemical
impedance spectra (Figure S4, Supporting Information). The
number is obviously higher when the mixed electrolyte is pre-
sent on the anode (tZn2+ = 0.72). The low tZn2+ (0.33) in common
liquid electrolyte causes a larger Zn2+ concentration gradient
near the anode, leading to the formation of interfacial electric
fields and dendrites growth.[18] Furthermore, the ZSM-5 elec-
trolyte membrane in symmetric cells shows obvious SEI
impedance, indicating that the solid–liquid mixed membrane
may also function as a SEI layer, which offers dynamic protec-
tion against Zn passivation.
To reflect the stability of the ZSM-5-based electrolyte
membrane, long-term galvanostatic cycling of the symmetric
cells was evaluated at a common current density and area
capacity (1  mA cm−2, 1  mA h cm−2) (Figure  2d). The ZSM-5
based symmetric cell exhibits an extended cycling lifetime for
over 2000  h, in comparison with 174  h for common ZnSO4
electrolyte with GF separator. In terms of CE, the Zn anode
in common ZnSO4 electrolyte shows unstable CE values after
200 cycles due to the side reactions. In contrast, the mixed
electrolyte membrane exhibits noticeably high reversibility
and stable plating/stripping behaviors with an average CE of
98.9%, which start to drop after ≈1000 cycles (Figure  2e). This
cyclic stability improvement accords with the proposal that the
ZnSO4−ZSM-5 mixed electrolyte regulates the surrounding
water activity and induce homogeneous Zn2+ diffusion.
2.2. Chemical Structure and Surface Adsorption Properties
As indicated above, the channel dimension of ZSM-5 provides
proper structure to regulate the activity of water molecules in
both electrolyte and Zn2+ solvation sheath. The nitrogen adsorp-
tion isotherm measured by Brunauer–Emmett–Teller indicates
that ZSM-5 has a high specific surface area of 407.8 m2 g−1, due to

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Figure 3.  Characterization and calculation of ZSM-5 electrolyte membrane. a) Nitrogen adsorption/desorption isotherm of ZSM-5. b) The inset is pore
width (channels size) distribution of ZSM-5. c) Adsorption principle of ZnSO4 solution on ZSM-5. d) Raman spectra of ZnSO4 solution and ZSM-5
mixed electrolyte membrane. e) Typical structural models of water adsorption by ZSM-5. f) Comparison of adsorption energies between H2O and
molecular sieve and between H2O and Zn2+.

its abundant channels (Figure 3a). The measured channel size of
ZSM-5 molecular sieve ranges from 0.54 to 0.64 nm (Figure 3b).
As shown in Figure S4, Supporting Information, Zn2+ in ZnSO4
solution generally coordinates six water molecules to form first
solvation sheath due to the strong polarization of H2O molecules,
and then associates with SO42− ions in a form of solvent isolated
ion pair (SSIP) [Zn2+(H2O)6·SO42−] (the diameter is 8.60 Å)
(Figure S5, Supporting Information).[1c,19] Zn2+ loses some water
molecules in first solvation sheath and directly contacts with
SO42− in a form of contact ion pair (CIP) [Zn2+(H2O)5·OSO32−].[20]
There are plenty of SiO and AlO bonds in the ZSM-5 mole-
cular sieve, in which O atoms can form hydrogen bonds with
water molecules. This feature allows the ZSM-5 molecular sieve
to absorb free water molecules in ZnSO4 solution and solvated
water molecules around Zn2+ (Figure 3c). To unveil the types of
Zn2+ inside molecular sieve, Raman spectra of ZnSO4 solution
and ZSM-5 electrolyte membrane were recorded (Figure  3d). A
classical broad peak of OH tensile vibration (HOHOH2 and
HOHOSO32−, 3100–3700 cm−1) exists in the Raman spectrum
of ZnSO4 solution. However, in the case of the mixed electrolyte
membrane, the broad peak of OH tensile vibration vanishes
and several small peaks appear in the 3400–3700 cm−1 range. The
disappearance of the OH broad peak indicates limited amount
of free water molecules in the ZSM-5 electrolyte membrane, and
hydrogen bonds between water molecules are weakened. These
small peaks correspond to OH bonds vibration of free water
molecules, solvated water molecules, and the hydrogen bonds
formed between them and molecular sieve. A new peak
(at 245 cm−1) is attributed to Zn2+-OSO32− vibration, indicating
the transformation of Zn2+ from SSIP to CIP form in ZSM-5. The
new peak at 290 cm−1 matches Zn2+-OSi/Al.[21] The stretching
vibration of SO42+ is slightly blue shifted, reflecting the destruc-
tion of solvated structure. In addition, the infrared spectrum of
GF and ZSM-5 electrolyte membrane (Figure S6, Supporting
Information) shows that the ZSM-5 electrolyte membrane has
weaker OH stretching vibration (at 3200–3400 cm−1) and H2O
molecule bending vibration (at 1630 cm−1), corroborating the
reduced activity of water molecules in ZSM-5 membrane.
Density functional theory calculation was conducted to
further investigate the adsorption of H2O to the ZSM-5 channels.
Due to symmetry, six configurations of H2O adsorption
are considered (Figure  3e). Positions far from Al atoms have
low adsorption energy and are more likely to adsorb H2O.
The adsorption energy between Zn2+ and H2O is −0.062  eV

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Figure 4.  Electrochemical performance of V2O5||ZSM-5||Zn full cell. Two electrolytes were employed: ZnSO4 electrolyte with GF separator and ZnSO4−
ZSM-5 mixed electrolyte membrane. a) CV curves at 1 mV s−1 at different cycles. b) Galvanostatic charge-discharge curves. c) Cycling performance
with corresponding Coulombic efficiencies at 1 A g−1 for 3000 cycles. d) Long-term cycle performance with corresponding Coulombic efficiencies at
the high current of 5 A g−1. e) Rate performance at different rates. f) Charge–discharge curves of GF and ZSM-5 full cells (1 A g−1, charging to 1.6 V,
standing for 24 h, and discharging to 0.2 V).

(Table S1, Supporting Information). At sites 2, 3, and 6, the
adsorption energy of ZSM-5 is greater than that of Zn2+,
implying that ZSM-5 is easier to adsorb water molecules than
Zn2+ (Figure  3f). Hence, the type of Zn2+ in ZSM-5 channels
is more likely CIP, and the channel structure suppresses water
molecule activity.
2.3. Performance in AZIB Full Cell
To further investigate the feasibility of the ZnSO4−ZSM-5
mixed electrolyte for practical applications, both GF separator
and ZSM-5 solid–liquid mixed electrolyte membranes are
employed for AZIB full batteries. Acid-treated V2O5 and Zn
foil were used as the cathode and the anode, respectively. X-ray
diffraction (XRD) patterns of V2O5 reflect the layered struc-
ture of the V2O5 crystal (Figure S7, Supporting Information).
Cyclic voltammetry (CV) of the ZSM-5 membrane full battery
(Figure 4a) shows that a pair of redox peaks appear at 1.31 and
0.93 V in the first three cycles, which then gradually disappear
in the subsequent cycles. Stable redox reactions appear at
0.84/1.15 V and 0.82/0.83 V. This phenomenon occurs frequently
in V2O5 cathode materials and it reflects the structural evolu-
tion of V2O5 during initial reaction.[22] The typical redox pairs
suggest that Zn2+ could intercalate/extract through the solid–
liquid mixed electrolyte membrane to the V2O5 cathodes. A
reasonable hypothesis is that the molecular sieve reduces the
size of the hydrated Zn2+ ions and makes them easier to enter
the layer space of V2O5 (spacing is 4.4 Å).[23] Hence, additional
treatment to increase the layer spacing of V2O5, such as the
introduction of water molecules or other organic molecules, is
not needed.[24] The ZSM-5 cell has four obvious charging and
discharging voltage platforms corresponding to the valency
changes of v3+→v4+→v5+ and v5+→v4+→v3+ (Figure  4b).[25] The
specific capacity did not change significantly from the 100th to
2000th cycles, only slightly decreasing until 3000 cycles, demon­
strating super stable electrochemical performance. At room
temperature, the saturation concentration of ZnSO4 solution is
about 3.3  m.[26] Compared to the 1  m and 2  m ZnSO4 electro-
lytes, the 3 m ZnSO4 soaked ZSM-5 membrane has the slowest

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capacity attenuation and the best cycle stability (Figure S8, Sup-
porting Information). This is due to a fact that there is less free
water in ZSM-5 electrolyte membrane when it is soaked in high
concentration ZnSO4, and the side reaction of the Zn anode is
minimized to the greatest extent. The excess water molecules
in low concentrations (1 m ZnSO4) occupy the adsorption sites
of the molecular sieve, resulting in faster capacity decay.
After 30 cycles of activation at 1 A g−1, both the specific capacity
of GF and ZSM-5 cells reaches their maxima (300 mAh g−1)
(Figure S9, Supporting Information). However, the capacity of
GF cell rapidly drops, by 50% at the 1000th cycle (Figure  4c).
In contrast, the ZSM-5 cell presents excellent cycle stability.
The capacity retention rate reaches 98% at 1000th and 82.67%
after 3000 cycles. The drastically enhanced cyclic stability of the
ZSM-5 cell is ascribed to the channel structure of the mixed
electrolyte which regulates the water activity and induces fast
and even diffusion of zinc ions. At a higher current level of
5 A g−1, the ZSM-5 battery still has a capacity retention rate of
82.4% after 15 000 cycles (Figure 4d). Note that the capacity of the
ZSM-5 cell keeps increasing for the initial 3400 cycles because
the activation process of V2O5 is prolonged under a large cur-
rent. Following that, the gradual decrease in capacity might
be due to many factors, including but not limited to incom-
plete extraction of Zn2+ from the cathode, slight dissolution
of the cathode into the electrolyte, and surface passivation due
to possible side reactions.[27] At a small current of 0.1 A g−1,
the capacity retention rate of ZSM-5 full cell was 92.1% after
100 cycles, while the capacity of GF full cell decayed rapidly
(Figure S10, Supporting Information). The rate performance of
the ZSM-5 cell is also excellent, with a capacity recovery rate of
96.9% from 0.5 C to 10 C. (Figure  4e; Figure S11, Supporting
Information). In addition, the self-discharge behavior of the
ZSM-5 membrane cell has also been significantly slowed down,
which is likely a consequence of the reduction of side reaction
and less dissolution of cathode materials in the solid–liquid
mixed electrolyte. After standing for 24  h, the capacity reten-
tion of ZSM-5 cell is 95.7% compared to 72.3% of the GF cell
(Figure 4f).
The ZSM-5 molecular sieve is physically stable and poten-
tially recyclable. After crushing, washing, filtering, and drying,
the recycled ZSM-5 electrolyte membrane was recovered in
the form of powder. Subsequently, the powder was pressed,
dried, and soaked as new electrolyte membranes. The XRD
patterns of the original and recycled ZSM-5 powder show that
the ZSM-5 molecular sieve maintains a constant lattice struc-
ture during battery cycles (Figure S12, Supporting Information).
The AZIBs constructed from a recycled ZSM-5 molecular sieve
still has comparable high capacity (347 mAh g−1) and cycle

Figure 5.  Characterization of Zn anodes after cycling. a) SEM images of the Zn anodes of the full cells with different cycle numbers at 1 A g−1 and an
area capacity of 1 mA h cm−2. Top: ZnSO4 electrolyte with GF separator; Bottom: ZnSO4−ZSM-5 mixed electrolyte membrane. b) XRD patterns of Zn
electrode sheets of Zn||ZSM-5||Zn symmetrical cells after different cycles at a current density of 1 mA cm−2. c) Schematic of zinc-ion deposition in the
two electrolytes.

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stability (capacity retention: 98.5% after 1000 cycles) (Figure S13,
Supporting Information). The recyclability of molecular-sieve
membrane may further lower the cost of battery fabrication.
2.4. Morphology Evolution of Zn Anode
To gain insight to the excellent cycling stability of ZSM-5-based
full cells, the morphology of the Zn anode after cycling at
1 A g−1 for different cycles was examined. As shown in
Figure 5a, when GF is used as a separator, many small dendrites
are formed due to nonuniform deposition. These dendrites will
generate uneven electric field distribution, and promote the
further growth into large dendrites due to preferential deposi-
tion of zinc ions. In terms of ZSM-5 electrolyte membrane, a
tiled Zn surface is observed due to the even distribution of
the electric field on the electrode surface as discussed above.
Subsequent zinc ions epitaxially deposit in the 002 planes of
these tiled surface and grow laterally, ensuring the flatness of the
Zn anode. XRD patterns (Figure 5b) also indicates the increase
in (002) texture. To summarize, the vertical versus lateral growth
of Zn flakes on the anode surface in the two electrolytes is illus-
trated in Figure 5c. Digital photos show clearly the uniform sur-
face of the Zn anode even after 1000 cycles in ZSM-5 electrolyte
compared to a patchy surface for Zn in GF and obvious corro-
sion after 1000 cycles (Figure S14, Supporting Information).
2.5. Other Molecular Sieves with Different Channel Sizes
In addition to ZSM-5, we investigated other molecular
sieves with sizes of 0.3–11  nm. The performance of full cells,
symmetrical cells, and Zn–Cu half cells of different molecular
sieves was systemically compared (Figure 6a,b; Figures S15,S16,
Supporting Information). It is determined that those with chan-
nels sizes in a narrow range of 5–7 Å, including ZSM-5, H-β,

Figure 6.  Molecular sieves with different channel sizes for AZIBs. a) Comparison of capacity retention rates (after 2000 cycles) and specific capaci-
ties of full cells. b) Cycling performance of Zn symmetric cells with various molecular-sieves-based electrolytes at the current density of 1 mA cm−2.
c) Wettability of various molecular-sieve membranes in ZnSO4 solution. d) Schematic of electrolyte in molecular-sieve channels. e) Nyquist plots of
ZSM-5 symmetric cells at different temperatures. The inset is corresponding Arrhenius plot. f) Calculated desolvation energy based on the charge-
transfer resistances.

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and Bate, show the best AZIB performances in terms of cycle
lifespans and capacity retention. To understand the reason to
different performance, the surface wettability of ZnSO4 solu-
tion and the conductivity of molecular-sieve electrolyte mem-
branes were examined. ZSM-5, H-β, and Bate membranes have
good surface wettability with contact angles slightly higher than
30°, whereas those 3–5 Å molecular-sieve membranes show
much poorer wettability (Figure  6c; Figure S17, Supporting
Information). The conductivities of the molecular-sieve elec-
trolyte membranes with channels sizes 3–5 Å are also inferior
(Figure S18, Supporting Information). When the channel size
is larger than 5 Å, the conductivities are close to that of GF elec-
trolyte membrane.
The ZnSO4 electrolyte in molecular-sieve channels are
depicted schematically (Figure 6d). The diameter of the solvated
zinc ions, Zn2+(H2O)6, is about 8.6 Å.[28] When the molecular-
sieve channels are 3–5 Å, it means the solvated zinc ions are
difficult to enter the molecular-sieve channels, corresponding to
the poor surface wettability and conductivity and subsequently
electrochemical performance. When the channel size of the
molecular sieve becomes large (>7 Å), more free water mole-
cules in channels preferentially occupy the absorption sites of
molecular sieves, and hinder the adsorption of the solvated
water molecules around the zinc ions (Figure S19, Supporting
Information). The optimal channel size is between 5 and 7 Å,
slightly smaller than the diameter of the solvated zinc ions.
Due to space restriction in the channels as well as the abundant
SiO bonds on the channel wall, the coordinated water mole-
cules in solvation sheath may be extruded. In other words,
the coupling of space limitation and channel wall adsorption
brings the molecular sieve with channel size of 5–7 Å the best
desolvation ability. Consequently, water exposure of the Zn
anode is reduced, resulting in fewer side reactions and a longer
cycle life compared to large of small size channels. In addition,
the desolvation energies (Ea) of Zn2+ during plating are calcu-
lated according to the charge-transfer resistances (Rct) of GF
and zeolite symmetric cells at different temperatures (Figure 6f;
Figure S20, Supporting Information). As expected, the mole-
cular sieves (ZSM-5, H-β, and Bate) with channels sizes of
5–7 Å have lower desolvation energy than those with smaller
and large channel sizes, suggesting the importance of choosing
suitable channel/pore sizes for effective regulation of the
solvation structure.
3. Conclusion
A unique solid–liquid mixed electrolyte has been introduced
to fabricate separator-free aqueous Zn-ion batteries with
improved zinc deposition behavior and substantially extended
cycle lifespan. The channel structure of the ZSM-5 molecular
sieve has a strong limiting effect on both free water and
zinc-ion-solvated water, and facilitates zinc-ion diffusion on
the Zn anode. The ZSM-5 solid–liquid mixed electrolyte mem-
brane effectively inhibits dendrite, hydrogen evolution, and
passivation of zinc anode. As a result, the battery cycle life
is remarkably prolonged. Specifically, the V2O5||ZSM-5||Zn
full-cell battery has a high specific capacity (300 mAh g−1)
and can maintain 98% of its initial capacity after 1000 cycles
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and 83% after 3000 cycles at 1 A g−1. Even at a high current of
5 A g−1, the full cell can run up to 15  000 cycles with 82%
capacity retention. For molecular sieves with varying channel
sizes, the coupling effect of space limitation and channel wall
adsorption needs to be considered. It is determined that the
molecular sieves (ZSM-5, H-β, and Bate) with the channel size
of 5–7 Å give the best desolvation capacity and cycle stability.
While this research suggests the promising application of
ZSM-5 molecular sieve as an electrolyte host for separator-free
aqueous batteries, further research can be carried out to achieve
a balance between mechanical stability and battery energy
density. Given that the thin ZSM-5 membrane is fragile, it is
necessary to design and improve the mechanical strength and
robustness of the solid–liquid mixed electrolyte membrane.
A possible strategy in future research is to develop adhesives
with better adhesion to molecular sieves. A roll-to-roll pressing
method would also be helpful for large-scale production.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (No. 22172103, 21773009). H.J.F. acknowledges financial support
from the Singapore Ministry of Education by Academic Research Fund
Tier 2 (MOE-T2EP50121-0006).
Conflict of Interest
The authors declare no conflict of interest.
Authors Contribution
W.S. and H.J.F. proposed and designed the research. J.Z. and Z.B. carried
out the fabrication of the electrode membrane and the whole cell. X.C.,
Z.J., Z.W., and J.T. conducted the characterization and electrochemical
measurements. J.Z. and Z.B. analyzed the data and co-wrote the
first draft. All authors discussed the results and commented on the
manuscript. J.Z., W.S., and H.J.F. revised the paper.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
aqueous Zn batteries, dendrites, molecular sieves, separator-free
batteries, Zn-anode stability
Received: August 8, 2022
Revised: August 29, 2022
Published online:
© 2022 Wiley-VCH GmbH
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