Chemical Engineering Journal 433 (2022) 133532

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Chemical Engineering Journal

Sustainable biopolymeric hydrogel interphase for dendrite-free aqueous

A R T I C L E I N F O A B S T R A C T

Keywords: Naturally derived hydrogels have emerged as advanced manufacturing materials due to their biosafety,
Biopolymer hydrogels biocompatibility, and eco-friendly property while retaining large amounts of water. Here, we demonstrate that
Electrolyte interphase biopolymeric hydrogel interphase derived from abundant natural polysaccharide exhibits successful stabilization
Zn metal anodes
of 3D structured Zn anodes for dendrite-free aqueous zinc-ion batteries (ZIBs). The cross-linked natural hydrogel
Aqueous zinc-ion batteries
Zinc dendrites
interphase on Zn anodes guides the uniform stripping/plating of Zn2+ for dendrite-free homogeneous Zn
deposition and effectively avoids direct contact between reactive aqueous electrolytes and Zn anodes, inhibiting
the parasitic side such as the hydrogen evolution reaction. Furthermore, the thin hydrogel interphase enables
employing liquid electrolytes without lowering volumetric energy density. Such characteristic allows high ionic
conductivity and, more importantly, significantly reduces cell resistance compared to previous ZIBs with only
hydrogel electrolytes. These features afford highly stable zinc plating/stripping behaviors at high areal current
density (10 mA cm− 2) and capacity (2 mAh cm− 2) for 1500 h, enabling durable cycle stability of full cells paring
with MnO2 cathodes during 3000 cycles at 2 Ag− 1 without capacity fading. Our strategy not only suggests a
“green” method for developing dendrite-free aqueous ZIBs but also provides natural polymers with expansion
into future aqueous energy storage fields.

1. Introduction abundance, and relatively low redox potential (-0.76 V vs. standard
hydrogen electrode) [4,5]. Moreover, high insensitivity to oxygen and a
Natural hydrogels derived from biopolymers such as natural poly­ humid atmosphere, and an excellent safety feature of aqueous electro­
saccharides can hold a large amount of water due to their three- lyte allow ambient battery assembly and lower manufacturing costs,
dimensional (3D) polymeric networks [1]. Their unique features such supporting that the aqueous ZIBs are suitable for large-scale ESSs [6].
as multi-functionality, biocompatibility, biodegradability, abundancy, Nevertheless, Zn metal anodes consistently suffer from dendrite
nontoxicity, low cost, and large surface area for multivalent bio­ formation and corrosion reactions when they directly contact corrosive
conjugation offer great potential for applications in many biomedical aqueous electrolytes, which seriously impedes the reliable operation of
fields [2]. Recently, biopolymer hydrogel electrolytes have attracted the aqueous ZIBs [7–11]. A recent study suggested that biopolymer
particular interest in developing aqueous batteries that employ aqueous hydrogel electrolytes alleviate these chronic problems of the Zn metal
electrolytes instead of flammable organic electrolytes. The biopolymer anodes, especially the dendrite formation and parasitic side reactions
hydrogel swollen by aqueous electrolytes offers unpar­ [12]. Nonetheless, the ionic conductivity of most hydrogel-based elec­
alleled opportunities to realize flexible aqueous batteries that trolytes is several orders of magnitude lower than that of aqueous
commonly experience large mechanical deformations (i.e., bending, electrolytes, an intrinsic limitation of hydrogel electrolytes. Further­
folding, twisting, and stretching) [3]. Among the aqueous batteries, the more, such hydrogel electrolytes could lead to relatively poor physical
aqueous zinc-ion batteries (ZIBs) are proposed as promising alternatives contact and interfacial instability at electrode/electrolyte interfaces,
to flammable lithium-ion batteries (LIBs) as large-scale energy storage especially at 3D structured Zn anodes, resulting in increased interfacial
systems (ESSs) with advantages of metallic Zn, including high theoret­ resistance compared to liquid electrolytes [13–15]. These limitations
ical specific capacity (820 mAh g− 1 and 5855 mAh cm− 3), high could be challenging since the ionic conductivity, and interfacial

* Corresponding author.
E-mail address: [email protected] (C. Kim).

https://doi.org/10.1016/j.cej.2021.133532
Received 5 September 2021; Received in revised form 23 October 2021; Accepted 6 November 2021
Available online 12 November 2021
1385-8947/© 2021 Published by Elsevier B.V.
 J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

stability are directly related to facile ion transport, which plays a critical electrolyte swelling in 2 M ZnSO4 + 0.1 M MnSO4 solution for 24 h was
role in reliable battery performances. On the other hand, with the use of followed. The thickness of the CA solid electrolyte was about 300 µm.
aqueous electrolytes, higher ionic conductivity and formation of stable
electrode/electrolyte interfaces thru complete contact between the two 2.3. Material characterization
reduce the equivalent series resistance [16]; hence, high rate capability
and power density are usually expected of the batteries with aqueous To characterize the surface and cross-sectional morphologies of
electrolytes than the hydrogel electrolytes. Unfortunately, both the ad­ samples, a field-emission scanning electron microscopy (FE-SEM,
vantages to the aqueous and hydrogel electrolytes have not been real­ MIRA3, TESCAN) operating at 10 kV and a Fourier transform infrared
ized in a single battery yet. spectrometer (FT-IR, AlphaII, Bruker) were used. To investigate the
Our proposed solution is to use a hydrogel protective layer for the sample crystallinity, X-ray diffraction (XRD, Empyrean, Malvern Pan­
metallic Zn anodes by taking advantage of the biopolymer hydrogel and alytical) with Cu Kα radiation (λ = 1.54056 Å) between 5◦ and 90◦ was
aqueous electrolytes. Agarose, a marine-based polysaccharide, forms a used. The wettability tests were carried out by the contact angle mea­
thin hydrogel protective layer (~10 µm) on the surface of the Zn anodes surement using a drop of electrolyte (2 M ZnSO4) with a drop volume of
via an environmentally friendly cross-linking process. In turn, the 10 µl.
agarose hydrogel protective layer provides excellent suppression of
dendrite growth by uniformly redistributing Zn2+ flux and significantly 2.4. Electrochemical measurements
reduces the activation energy, leading to dendrite-free Zn anodes.
Moreover, preventing direct contact with aqueous electrolytes avoids The α-MnO2 was prepared by a typical hydrothermal synthesis as the
the corrosion reactions of the metallic Zn, resulting in highly improved cathode material. In brief, 0.003 mol of MnSO4⋅H2O and 2 ml of 0.5 M
electrochemical stability and reliable battery operation. More impor­ H2SO4 were added to 60 ml DIW and magnetically stirred until a clear
tantly, the hydrogel protective layer enables the use of aqueous elec­ solution was obtained. Then, 20 ml of 0.1 M KMnO4 aqueous solution
trolyte solution without lowering ionic conductivity and cell resistances was slowly added into the pre-mixed solution. The mixture was stirred at
which are the critical limitations of typical thick-hydrogel electrolytes. room temperature for 1 h and subsequently transferred to a Teflon-lined
Overall, the aqueous ZIBs with the protective layer coated Zn anodes autoclave and heated at 120 ◦ C for 12 h. After cooling and centrifuga­
deliver a high capacity (111 mAh g− 1) and maintain excellent retention tion, the α-MnO2 was rinsed three times with DIW and ethanol several
of 94% at 2 A g− 1 after 3000 cycles. times and then dried using a convention oven at 80 ◦ C for overnight.
Next, the α-MnO2 were cast on titanium (Ti) foil and composed of three
2. Experimental components: active material (α-MnO2), conductive materials, and
binder in the weight ratio of 7:2:1. Super-P carbon black and poly­
2.1. Preparation of electroplated Zn anodes vinylidene fluoride were selected as the conductive material and the
binder, respectively. Slurries containing the three components in N-
All commercially available reagents and solvents were purchased methyl-2-pyrrolidone were cast onto Ti foil (10 µm thick) via the doctor
from Merck and used as received without further purification. The blading method, followed by a drying step at 100 ◦ C for 12 h under
electrodeposition bath was prepared by dissolving 30 g of ZnCl2, 60 g of vacuum. The active mass loading for the cathode material was ~ 2 mg
potassium chloride (KCI), and 9 g of boric acid (H3BO3) in 300 ml of de- cm− 2. Pouch-type cells were assembled in air ambient atmosphere by
ionized water (DIW). The electrodeposition of Zn was carried out using a sandwiching glass fiber as a separator (Whatman) soaked with electro­
two-electrode cell. A platinum mesh (6 cm2) was used as a counter lyte (2 M ZnSO4 + 0.1 M MnSO4 aqueous electrolyte) between the
electrode, and a pristine zinc foil (100 μm thick) was used as a working cathodes and Zn anodes. For comparison, the freestanding CA solid
electrode. After two electrodes were immersed into the solution, and electrolyte was inserted between electrodes instead of a separator and
galvanostatic deposition of Zn was carried at a current density of 40 mA packaged as pouch-type cells without injection of liquid electrolyte.
cm− 2 for current-on and current-off time of 1 s and 2 s, respectively. All galvanostatic measurements were tested using a WBCS-3000
After 600 cycles, the electrodeposited Zn films were rinsed with DIW battery cycler (Wonatech) in the potential window of 1–1.8 V at
several times, then ethanol, and dried at a convection oven at 80 ◦ C for 25 ◦ C. For symmetric cells, 2 M aqueous ZnSO4 solution without MnSO4
30 min. additives is used as electrolyte. Linear polarization and chronoampero­
grams (CAs) measurements were conducted in a three-electrode
2.2. Preparation of hydrogel protective layer coated Zn anodes and CA configuration with a Pt foil as the counter electrode and an Ag/AgCl
solid electrolytes electrode as the reference electrodes (conducted using ZIVE SP1) at
20 ◦ C. Hydrogen evolution reaction of anodes was determined in 1.0 M
0.5 g of agarose, 0.05 g of glycerol (C3H8O3), 0.01 g of citric acid Na2SO4 by line sweep voltammetry (LSV) measurement with a three-
(C₆H₈O₇), and 0.01 g of sodium hypophosphite monohydrate (NaH2 electrode system (conducted using ZIVE SP1) at a scan rate of 1 mV
PO2⋅H2O) were added into 50 ml of DIW. Then, the mixture was placed s− 1 in a voltage range of − 1.0 to − 1.9 V versus Ag/AgCl. The electro­
inside a conventional microwave and heated at 700 W for 20 s. By chemical impedance spectroscopy (EIS) for evaluating transference
repeating the process once more, a transparent solution was achieved. number and ionic conductivity were obtained in the frequency range of
Then, the electroplated Zn anode was vertically immersed into the so­ 10-2 – 106 Hz (at an AC voltage of 5 mV amplitude for transference
lution and kept in a convection oven at 80 ◦ C for 12 h. Then, thermal number, 1 mV amplitude for ionic conductivity) using a potentiostat
cross-linking was conducted in a vacuum oven at 120 ◦ C for 2 h. Finally, (ZIVE MP2A, Wonatech) at 25 ◦ C. The hydrogel-based protective layer
hydrogel-based protective layer coated Zn anodes were prepared after was sandwiched between stainless steel blocking electrodes in electro­
electrolyte injection and aging of fabricated ZIBs for 24 h. The free­ lyte and obtained a typical Nyquist plot in the frequency range from 1 Hz
standing CA solid electrolyte was prepared in a concentrated solution. to 1 MHz. Then, the ionic conductivity of the artificial SEI layer was
2.5 g of agarose, 0.5 g of glycerol, 0.25 g of citric acid, and 0.125 g of calculated from the following equation [17]:
sodium hypophosphite were added into 50 ml of DIW. Then, the mixture
was placed inside a conventional microwave and heated at 700 W for 20 l
σ=
s. By repeating two more times, a transparent solution was achieved. R∙A
Subsequently, the transparent solution was poured into an evaporating where l is the thickness of the hydrogel-based protective layer (300
dish and kept in a convection oven at 80 ◦ C for 12 h. Then, thermal cross- μm), A is the contact area (4.5 cm− 2), and R represents the resistance
linking was conducted in a vacuum oven at 120 ◦ C for 2 h. Subsequently, according to the EIS measurement (0.74 Ω at 25 ◦ C).

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J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

The activation energy (Ea) is calculated based on the Arrhenius agarose content (1 wt% in water).
equation [18]: 3D porous structuring of Zn metal anodes has been demonstrated to
( ) decrease overpotential by increasing effective surface areas of metal
1 Ea
= Aexp − electrodes and depress the dendrite growth [28]. Therefore, employing
Rct RT
the 3D porous structure for the Zn anode can compensate for increasing
where Rct is the charge transfer resistance, A is the pre-exponential overpotential by coating the agarose hydrogel. We prepared 3D porous
constant, T is the absolute temperature, and R is the standard gas structured Zn metal anodes (hereafter, E-Zn) via a simple pulsed elec­
constant. trodeposition method. Then, the agarose hydrogels were coated on the
surface of the E-Zn, as illustrated in Fig. 1d. During the electrodeposition
3. Results and discussion process, plate-like Zn electrodeposits with macro-pores were formed on
a Zn foil (Fig. 2a). Both the bare-Zn and E-Zn illustrate the same peak
Agarose is one of the most commonly used biopolymer hydrogels, positions (PDF# 01–078-702) but slightly different peak intensities
being easily extracted from seaweeds, as a linear polysaccharide con­ (Fig. S3). After agarose coating, a flat surface without noticeable defects
sisting of d-galactose and 3,6-anhydro-L-galactopyranose linked by α-(1 was observed (rather than the morphology of the E-Zn), indicating the
→ 3) and β-(1 → 4) glycosidic bonds (Fig. 1a and S1) [19–21]. Agarose formation of the conformal agarose coating layer (Fig. 2b). Energy-
has relatively fewer charged functional groups and easily forms hydro­ dispersive X-ray spectroscopy (EDS) mapping images of the cross-
gel with high water content (greater than90% water). The agarose linked agarose (abbreviated as CA) coated on E-Zn (hereafter, E-
hydrogel is a highly elastic, moldable, and biocompatible medium with Zn@CA) exhibited a uniform distribution of O, C, and Zn across the
high ion mobility, used for gel electrophoresis for separating DNA entire area, supporting the formation of the uniform CA protective layer
[22–24]. To employ agarose as a hydrogel-based protective layer for Zn (Fig. 2c). The cross-sectional SEM image shows that the thicknesses of
anodes, the hydrogel network should be cross-linked to prevent the electrodeposited Zn and CA layers were almost the same as about 10
decomposition of the hydrogel protective layer by aqueous electrolytes. µm, respectively (Fig. 2d). In order to clearly show the CA layer coated
In this work, agarose was chemically cross-linked with citric acid, which 3D porous surface of E-Zn, we spotted the crevice between E-Zn and the
emerged as a non-toxic cross-linking agent for the preparation of CA protective layer (Fig. S4). The CA protective layer, however, is
hydrogels [25]. The Fourier-transform infrared (FT-IR) spectra of the actually well coated on the surface of E-Zn, as shown in Fig. S5. This
cross-linked agarose shows a sharp absorption band at 1664 cm− 1, observation is clearly distinguished from typical thick hydrogel elec­
indicating ester linkage due to the esterification reaction between hy­ trolytes shown in previous works [29–31]: reaching a few hundreds of
droxyl and carboxylic acid groups in agarose and citric acid, respec­ micrometers thick or even thinker than a few millimeters. In general, the
tively, during the cross-linking reaction (Fig. S2). The broad absorption lower thickness of inactive components of batteries is beneficial for
band near 3441 cm− 1 is derived from hydroxyl and carboxyl groups in improving the volumetric energy density, which offers the incorporation
CA protective layer [26]. In addition, glycerol was added as a plasticizer of more active materials into a fixed volume of electrodes for high en­
which also participated in cross-linking reaction and competing with ergy density. In this respect, substituting the thin CA protective layer for
agarose, resulting in less cross-linking and crystallization of agarose thick hydrogel electrolytes is quite advisable. After swelling electrolytes,
hydrogel to increase ionic conductivity [27]. As shown in Fig. 1C, the the thickness of the CA layer only extended to be ~ 30 µm, which is still
cross-linked hydrogel was successfully formed even at a very low thinner than the conventional thick hydrogel electrolytes. The stability
of the CA layer in the electrolyte was confirmed by SEM and EDS

Fig. 1. a) Digital photograph of red seaweed. b) Chemical structure of CA protective layer. c) Digital photograph showing elasticity of CA hydrogel. d) Schematic
illustrations showing the preparation of E-Zn@CA.

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J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

Fig. 2. a) SEM image of E-Zn. b) SEM and c) EDS elemental (O, C and Zn) mapping images of E-Zn. The scale bar in Fig. 2c is 30 µm. d) Cross-sectional SEM image of
E-Zn@CA. Contact angles of e) E-Zn@CA and f) bare-Zn with 2 M ZnSO4 electrolyte. g) AC impedance spectroscopy of CA protective layer and ionic conductivity.

mapping, as shown in Fig. S6. noteworthy because the thin CA layer successfully endowed the cells to
It is known that enhanced surface wettability contributes to a higher improve Zn2+ mobility instead of using thick hydrogel electrolytes.
Zn2+ distribution across the surface of Zn anodes with lower charge 3D structured Zn anodes with the expanded surface area can
transfer resistance during charge/discharge processes [17]. Moreover, considerably reduce the localized current density and overpotential,
the hydrophilic surface can reduce the interfacial free energy between leading to suppression of Zn dendrite formation [39,40]. As shown in
Zn anodes and electrolytes, leading to homogeneous zinc plating and Fig. S8a, symmetrical cells with the E-Zn exhibited substantially low
nucleation [32]. To examine the hydrophilicity of E-Zn@CA with polarizations of ≈ 90 mV and overpotentials under a high current den­
respect to the electrolytes, contact angle measurements at an ambient sity of 10 mA cm− 2 (areal capacity: 2 mAh cm− 2). By contrast, sym­
temperature of 25 ◦ C have been conducted. As shown in Fig. 2e and f, the metrical cells with bare-Zn suffered from large polarizations with
CA layer significantly improved surface hydrophilicity because of the overpotentials and eventually failed before 20 h due to a short circuit.
presence of the polar functional groups, hydroxyl (–OH), and carboxylic Unfortunately, fluctuation on the voltage profile and internal short-
acid (–COOH) groups. Also, the CA layer showed an ionic conductivity circuit signals (sudden voltage drops) were observed after 151 h in E-
of 9.52 × 10-3 S cm− 1, which was slightly lower compared to recently Zn cells, resulting in cell failure (Fig. S8b) [41]. To investigate the reason
reported hydrogel electrolytes (Fig. 2g) [3,29,33]. However, the thick­ for the failure, we disassembled the cycled symmetrical cells and
ness of the CA protective layer was still considerably lower than that of analyzed Zn anodes using ex-situ SEM micrographs (Fig. S8c-h). After 90
the previously reported hydrogel electrolytes, which helps reduce the h cycling, micrometer-scale Zn dendrites were vertically formed on the
equivalent series resistance. In addition, employing liquid electrolytes pure Zn, which pierced through the separator and induced an internal
contributes to reducing the thickness and cell performance. short circuit. On the contrary, shapes of the E-Zn were relatively well
Besides ionic conductivity, Zn2+ transference number is another maintained with micro crevice patterns rather than dendrite formation,
factor determining cell performances, especially, overpotential of the implying reversible zinc stripping/plating reactions occurring upon the
symmetric cell [34]. In particular, for aqueous zinc-ion batteries, a high E-Zn. However, we observed small but prominent Zn dendrites on the
Zn2+ transference number (t+) can guarantee a uniform ion distribution surface of E-Zn after 180 h. Although the 3D structures of the E-Zn
at the Zn anode interface [35]. Fig. S7 exhibits the Nyquist plots of significantly reduced the overpotential and mitigated the formation of
symmetric cells with E-Zn@CA and bare-Zn. The cell with bare-Zn the Zn dendrites, it was impossible to suppress the dendrite growth
showed a low Zn2+ transference number (t+) of 0.37, similar to previ­ completely.
ous studies. The low t+ stem from electrolytes where the counter anion Several previous works have confirmed that the hydrogel electro­
(SO42-) is highly mobile, while migration of the electrochemically active lytes suppressed the Zn dendrite formation by inhibiting localized zinc
Zn2+ is more sluggish due to its bulky solvation shell [36]. Conse­ metal nucleation and growth [29,30,33]. However, high interface and
quently, the concentration gradient occurs in the electrolyte, which in­ equivalent series resistances with hindered ionic conductivity always
duces the batteries’ insufficient charge/discharge limit and leads to crowd the hydrogel polymer electrolytes to replace liquid electrolytes.
concentration overpotential, eventually resulting in retarded energy and Nonflammable aqueous electrolytes altogether remove risks of fire
power densities of batteries [37]. On the contrary, the CA protective hazards which are the primary reason for employing solid electrolytes in
layer allowed a large Zn2+ transference number of 0.75, which implies LIBs. Therefore, the choice of hydrogel polymer electrolytes in the
the effective migration of Zn2+. The specific polar functional groups in aqueous ZIBs is valid for limited small applications requiring flexible or
the CA layer may enhance the zinc salt (ZnSO4) dissociation [38]. stretchable functions and those unsuitable for large-scale ESS, which is
Furthermore, the hydroxyl groups in the CA layer form immobilize needed to maximize performances. In this regard, employing the CA
counter anions (SO42-) by forming strong hydrogen bonds [26]. Thus, we protective layer shows the best hydrogel and liquid electrolytes, allow­
achieved the high Zn2+ transference number (0.75), which is ing high ionic conductivity with effectively suppressing zinc dendrites

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J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

for the aqueous ZIBs. As shown in Fig. 3a, the symmetric cell with E- rampant 2D diffusion process and uneven Zn dendrite growth. To
Zn@CA remains stable at a suppressed polarization of 300 mV for a long- visually highlight modulating Zn plating morphologies, Zn deposition
life cycle of 1500 h under a high current density of 10 mA cm− 2, a morphology of bare and E-Zn@CA was observed by in situ optical mi­
considerably harsh condition compared to previous works (Table S1). croscopy at an extremely high current density of 30 mA cm− 2 (Fig. 3c
The symmetrical cell with bare-Zn@CA also showed stable zinc strip­ and d) [17,37,41–45]. A small dendrite formation on the surface of the
ping/deposition cycle, which directly confirms the effectiveness of the bare-Zn was clearly observed within 12 min, which is typically observed
CA protective layer (Fig. S9). Remarkably, the CA protective layer still after more than 20 min. Even worse, the small dendrites eventually
covered the E-Zn without dendrites after cycling for 1500 h under evolved into huge protuberances after 1 h, which can pierce separators
extreme conditions, as clearly seen in Fig. 3b. Furthermore, the sym­ and ultimately lead to typical battery failure. On the other hand, E-
metrical cells with E-Zn@CA maintained stable polarization curves with Zn@CA showed considerably different surface morphologies where the
reduced overpotentials compared to those with bare-Zn under step-up Zn was evenly plated with no visible dendrite growth under the high
current densities from 2 to 40 mA cm− 2 (Fig. S10). current applied even for 1 h. The cross-sectional SEM images clearly
The Zn deposition behavior of E-Zn@CA was investigated by chro­ showed the different Zn deposition morphologies between bare-Zn and
noamperometry (CA) measurements (Fig. S11). The nucleation and E-Zn@CA, as shown in Fig. 3 e,f. The CA layer efficiently covered the Zn
dendrite formation on the Zn surface are reflected by current variation deposits and suppressed dendrite penetration after Zn deposition at a
resulting from applied overpotential. Compared to previous works, a current density of 30 mA cm− 2 for 6 min. On the contrary, sharp Zn
relatively high overpotential of − 300 mV was applied for 150 s. E- dendrites and fragments were observed on the surface of bare-Zn. These
Zn@CA exhibited a highly suppressed current compared to bare-Zn, results indicate that the CA layer offers a uniform distribution of Zn2+ on
implying a stable 3D diffusion of Zn2+ after the short initial Zn nucle­ the anode surface, which effectively inhibits the dendrite formation.
ation and 2D diffusion processes. On the other hand, the gradually The low activation energy of E-Zn@CA can support another evidence
increasing current of bare-Zn during 150 s was observed, indicating a for the effective Zn2+ diffusion through the CA protective layer [46]. In

Fig. 3. a) Long-term galvanostatic cycling performances of symmetrical E-Zn@CA and bare-Zn cells at a current density of 10 mA cm− 2 (areal capacity: 2 mAh
cm− 2). b) SEM images E-Zn@CA after Zn plating/stripping cycles. In situ observations of Zn deposition by optical microscopy in symmetric cells composed of c) bare-
Zn and d) E-Zn@CA at a current density of 30 mA cm− 2. Cross-sectional SEM images of e) E-Zn@CA and f) bare-Zn after Zn deposition at a current density of 30 mA
cm− 2 for 6 min.

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principle, the strong Coulombic interactions between the solvated Zn2+ electrolyte can inhibit the dissolution of Mn2+ dissolution from the
and their surrounding solvent shells cause significant desolvation pen­ α-MnO2 [40]. As shown in Fig. S19 voltage polarization of 0.22 mV
alties at the electrode–electrolyte interface, which is typically consid­ between redox potentials (1.38/1.60 V) of the E-Zn@CA is smaller than
ered the rate-limiting step for Zn deposition with large activation energy that of bare-Zn (0.28 mV from redox potentials of 1.36 and 1.64 V) at a
[42]. The E-Zn@CA, however, exhibited much lower charge transfer scan rate of 0.1 mV s− 1, confirming the facile ion transport kinetic on the
resistances at all temperature ranges compared to bare-Zn, implying surface of E-Zn by employing the CA protective layer. The full cells with
facile charge transfer at anodes surfaces and resulting in much lower E-Zn@CA and bare-Zn showed similar discharge capacities of 304 and
activation of Zn stripping/plating (Fig. S12) [47]. Moreover, the polar 293 mAh g− 1, respectively, at a current density of 0.2 A g− 1 (Fig. 4a).
functional groups such as hydroxyl (–OH) and carboxylic acid (–COOH) The excellent electrolyte retention and significantly reduced activation
groups of the CA layer improve electrolyte wettability on Zn anodes and energy owing to the hydrophilic polar functional groups in the CA
remove Zn2+ solvation sheath, also contributing to facile ion transfer hydrogel protective layer allow facile migration channel for large ionic
kinetics and decreasing energy barrier compared to bare-Zn [48]. transport, resulting in highly improved capability for the full cell with E-
Consequently, homogeneous Zn deposition without dendrite formation Zn@CA [29]. By contrast, the full cell with the E-Zn@CA exhibited
was observed in the E-Zn@CA. considerably improved capacities compared to the cells with bare-Zn
Hydrogen evolution reaction (HER) on the Zn metal surface, usually throughout the broad range of current densities from 0.5 to 5 A g− 1,
accompanied by metal corrosion, is another major problem in devel­ except for initial activation for 10 cycles at 0.2 A g− 1, which sometimes
oping ZIBs [12]. The HER increases pH and local OH– concentration, appear at surface-modified Zn anodes (Fig. 4b) [28,42,51]. Notably, the
leading to the formation of by-products such as Zn oxides, Zn hydrox­ full cell with the E-Zn@CA retained 143 and 105 mAh g− 1 even at very
ides, and zincates and deterioration of cell performances by surface high current densities of 2 and 5 A g− 1, respectively, which correspond
passivation [40]. Constructing the CA protective layer on the surface of to 47% and 35% of its initial capacity at 0.2 mA g− 1. By contrast, bare-Zn
E-Zn effectively inhibits the HERs and corrosion reactions by eliminating only resulted in 85 and 50 mAh g− 1 at current densities of 2 and 5 A g− 1,
direct contact from active aqueous electrolytes (Fig. S13). By contrast, E- respectively, corresponding to 29% and 17% of its initial capacity at 0.2
Zn was vulnerable to HER. Interestingly, E-Zn showed the lowest onset mA g− 1.
potential of the HER due to the increased surface area compared to bare- Subsequently, cycling performances and CEs of the full cells were
Zn, which usually accelerates corrosion and HER [49]. The effective measured at a low and a high current density of 0.5 and 2 A g− 1,
inhibition of E-Zn@CA’s HER was also confirmed by reducing the gen­ respectively (Fig. S20 and Fig. 4c). The full cell with E-Zn@CA showed
eration of Zn4SO4(OH)6⋅xH2O by-products (Fig. S14) [37]. better cycle stability than the full cell with bare-Zn under low and high
To further verify the ability to suppress the side reaction of the CA current densities. In particular, after stabilization and activation during
protective layer, linear polarization experiments were also performed in the initial 200 cycles, the full cell with E-Zn@CA retained durable cycle
an electrolyte (2 M ZnSO4), as shown in Fig. S15. The corrosion potential stability for 3000 cycles. In particular, the full cell with E-Zn@CA
of bare-Zn and E-Zn obtained from Tafel extrapolation of polarization exhibited a high reversible capacity of 111 mAh g− 1 with durable ca­
curve were similar (-0.9778 V for bare-Zn, − 0.9790 V for E-Zn). Inter­ pacity retention of 94% (corresponding to an average capacity decay of
estingly, E-Zn@CA showed a higher corrosion potential of − 0.9686 V, 0.002% per cycle) compared to the capacity of the 200th cycle. This
suggesting the suppressed corrosion reactions and rates compared to value is the highest performance among the previously reported works
bare-Zn and E-Zn. about stabilizing Zn anodes using MnO2 cathodes (Table S2). Further­
The Coulombic efficiency (CE) is one of the critical considerations for more, CE of E-Zn@CA after 3000 cycles reached 99.9%, implying that
evaluating the reversibility of Zn during repeated cycling, which highly the artificial SEI layer significantly contributed to the excellent revers­
depends on the degree of side reactions [42]. The CE of Zn metal anodes ibility of the full cell. The full cell with bare-Zn@CA also exhibited
was evaluated by assembling Cu||bare-Zn and Cu||E-Zn@CA half cells durable cycle stability for 800 cycles, which indicates that the CA pro­
under a current density of 5 mA cm− 2 with a limited areal capacity of 1 tective layer significantly contributed to the cycling performance
mAh cm− 2. As shown in Fig. S16a and b, the half cell with E-Zn@CA (Fig. S21). On the other hand, the full cell with bare-Zn rapidly degraded
showed a slight initial polarization of ≈94 mV and higher CE than the during the initial 400 cycles. It only displayed 41 mAh g− 1 at the 800th
half-cell with bare-Zn. The striking differences are observed under an cycle, attributing to a short circuit resulting from the formation of
extremely high current density of 40 mA cm− 2 with a limited areal ca­ pierceable Zn dendrites.
pacity of 1 mAh cm− 2 (Fig. S17). The half cell with bare-Zn exhibited a To clarify the effective suppression of zinc dendrites by the CA pro­
large initial polarization of ≈229 mV, and the voltage was not fully tective layer, we further disassembled cells after initial 400 cycles at a
recovered at 1 mAh cm− 2 at the 70th cycle due to an internal short current density of 2 A g− 1. We scrutinized the surface of Zn anodes via
circuit. In contrast, the half cell with E-Zn@CA displayed the suppressed post-mortem analyses using a SEM analysis. As expected from the poor
initial polarization of ≈175 mV compared to the half cell with bare-Zn. electrochemical cycle performances, zinc dendrites nearly perpendic­
More importantly, the half cell with E-Zn@CA showed almost the same ular to the Zn metal plane densely covered the bare-Zn (Fig. 4d). In
voltage hysteresis from the 500th to 1000th cycle, with higher CE striking contrast, the CA protective layer covered the surface of E-Zn
reaching 99.8%. Meanwhile, under low current density (5 mA cm− 2), well, and no dendrite was observed (Fig. 4e and S22). The full cell with
the side reactions at Zn metal anodes become more severe during the E-Zn@CA also exhibited higher Zn2+ diffusion coefficient values than
longer cycle period, leading to low Zn utilization and the high self- bare Zn in most charge ranges, as shown in Fig. S23, which implies that
discharge rate with the low coulombic efficiency [50]. On the con­ the CA protective layer contributed to improving the kinetics of ion
trary, the corrosion and self-discharge rates are relatively mitigated diffusion in full cells, which leads to the superior electrochemical per­
under the high current density of 10 mA cm− 2 at the same capacity limit formance of the full cell with E-Zn@CA. Further details of the electro­
(1 mAh cm− 2), which is about 8 times shorter cycle period than that of chemical kinetics are described in Fig. S23. These observations clearly
high current density. These observations indicate that the CA protective indicate that the CA protective layer effectively inhibits the dendrite
layer successfully suppressed parasitic side reactions, promoting the formation by uniform deposition of solvated Zn2+ ions on the surface of
reversible Zn plating/stripping. electrodes. As a result, the E-Zn@CA showed excellent electrochemical
To explore the feasibility of the E-Zn@CA as an anode for the performances. Meanwhile, a self-discharge phenomenon is commonly
aqueous ZIBs, full cells were assembled with α-MnO2 cathodes, which observed in aqueous batteries, which deteriorates CE and leads to irre­
are the most widely used cathode material for the aqueous ZIBs versible water consumption and concentration change in electrolytes
(Fig. S18). A mixed aqueous solution of 2 M ZnSO4 + 0.1 M MnSO4 was [52]. In addition, the superiority of the CA protective layer for pre­
used as an electrolyte. The addition of the MnSO4 to the ZnSO4 venting self-discharge was evaluated by measuring discharge capacities

6
J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

Fig. 4. a) Galvanostatic charge/discharge voltage profiles at a current density of 0.2 A g− 1 (the 10th cycle). b) Rate capability and c) long-term cycling performances
at a current density of 2 A g− 1. SEM images d) bare-Zn and e) E-Zn@CA after 400 cycles. f) Self-discharge test by resting for 48 h at fully charged states after 10 cycles
at 0.2 A g− 1.

after 72 h of storage of full cells, which was charged to 1.8 V (Fig. 4f). leading to poor electrolyte/electrode interface contacts. As a result, the
After storing for 72 h, the full cell with bare-Zn showed only 77% of the full cell with CA solid electrolyte showed retarded cycle stability and
original capacity, which was mainly attributed to the parasitic side and large resistances compared to the full cell with CA protective layer and
corrosive reactions. On the contrary, a highly suppressed self-discharge liquid electrolyte. On the contrary, the CA protective layer is con­
rate of 3.3% was observed in the full cell with E-Zn@CA, which clearly formally formed on the E-Zn, and the liquid electrolyte allows the stable
demonstrates that the CA protective layer effectively lessens the side electrolyte/electrode interface. Furthermore, the CA protective layer
reactions and notorious dendrite growth. effectively prevents Zn anodes from not only the dendrite formation but
To demonstrate the effectiveness of our approach, full cells consist­ also side reactions. The improved surface hydrophilicity from the polar
ing of the E-Zn with CA solid electrolyte were prepared for comparison functional groups in the CA protective layer guarantees uniform distri­
with the protective CA layer with liquid electrolytes. As shown in bution of solvated Zn ions on the surface of Zn anodes and guides
Fig. S24, a flat surface was observed, and the residual aqueous electro­ migration of the Zn2+, effectively suppressing rampant propagation of
lyte was not observed. Furthermore, energy-dispersive X-ray spectros­ pierceable Zn dendrites on the surface of Zn anodes. In addition, the CA
copy (EDS) mapping images of the CA solid electrolyte exhibited a protective layer effectively avoids direct contact between reactive
uniform distribution of O, C, Zn, S, and Mn across the entire area, which aqueous electrolytes and Zn anodes, inhibiting the parasitic side re­
indicates that the freestanding CA solid electrolyte kept the ZnSO4 and actions. These results strongly support the superiority of the synergistic
MnSO4 inside. As can be seen in Fig. 5a, although both full cells showed combination of the surface hydrogel protective layer and liquid elec­
durable capacity retention during the long-term cycling test, the full cell trolytes for enhancing the electrochemical performances of aqueous
with the hydrogel electrolyte showed lower reversible capacity and ZIBs.
gradual degradation compared to the full cell with E-Zn@CA in the long-
term cycle test at a high current density of 2 A g− 1. Furthermore, the full 4. Conclusion
cell with the hydrogel electrolyte showed considerable charge transfer
resistance compared to the full cell performances with E-Zn@CA, which In summary, biopolymeric hydrogel-based interphase was developed
indicates that employing liquid electrolytes with a hydrogel protective as a surface protective layer on 3D structured Zn anodes to build highly
layer significantly reduced cell resistance (Fig. 5b and S25). As shown in stable ZIBs. Agarose, one of the abundant natural polysaccharides, can
Fig. 5c, the CA solid electrolyte does not fully and uniformly cover E-Zn, form a thin hydrogel protective layer on the surface of the Zn anodes via

7
J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

Fig. 5. a) Long-term cycling performances and b) Nyquist plot of ZIBs with different electrolytes at a current density of 2 A g− 1. c) Schematic illustrations showing
that the CA protective layer suppresses side reactions and dendrite formation with stable electrolyte/electrode interface.

an environmentally friendly cross-linking process. The CA protective Korea (NRF) grant funded by the Korea government (MSIT) (NRF-
layer was conformally coated on 3D structured Zn anodes, which guided 2020R1C1C1004322).
uniform deposition of solvated Zn2+ on the surface of electrodes for
dendrite-free homogeneous Zn deposition. Furthermore, the CA pro­ Appendix A. Supplementary data
tective layer effectively protected 3D structured Zn anodes from active
aqueous electrolytes, inhibiting the parasitic side reactions and self- Supplementary data to this article can be found online at https://doi.
discharge. Notably, the synergistic combination of employing the CA org/10.1016/j.cej.2021.133532.
protective layer and liquid electrolytes significantly contributed to
enhancing electrochemical performances of aqueous ZIBs without References
lowering ionic conductivity and increasing cell resistances which are the
critical limitations of typical thick-hydrogel electrolytes. Consequently, [1] Q. Huang, Y. Zou, M.C. Arno, S. Chen, T. Wang, J. Gao, A.P. Dove, J. Du, Hydrogel
scaffolds for differentiation of adipose-derived stem cells, Chem. Soc. Rev. 46 (20)
E-Zn@CA showed highly stable zinc plating/stripping behavior at high (2017) 6255–6275, https://doi.org/10.1039/C6CS00052E.
areal current density and capacity (10 mA cm− 2/ 2 mAh cm− 2) for 1500 [2] J.K. Oh, D.I. Lee, J.M. Park, Biopolymer-based microgels/nanogels for drug
h. Moreover, the full cell with E-Zn@CA showed highly durable cycle delivery applications, Prog. Polym. Sci. 34 (12) (2009) 1261–1282, https://doi.
org/10.1016/j.progpolymsci.2009.08.001.
stability (94% of the capacity retention) after 3000 cycles at a current [3] M. Chen, J. Chen, W. Zhou, X. Han, Y. Yao, C.-P. Wong, Realizing an all-round
density of 1000 mA g− 1. Overall, our approach could open research hydrogel electrolyte toward environmentally adaptive dendrite-free aqueous Zn-
avenues for developing highly stable and reversible aqueous ZIBs as Mno2 batteries, Adv. Mater. 33 (9) (2021) 2007559, https://doi.org/10.1002/
adma.v33.910.1002/adma.202007559.
large-scale energy storage systems but also be extended to the other [4] T. Zhang, Y. Tang, S. Guo, X. Cao, A. Pan, G. Fang, J. Zhou, S. Liang, Fundamentals
battery chemistries employing Zn. and perspectives in developing zinc-ion battery electrolytes: a comprehensive
review, Energy Environ. Sci. 13 (12) (2020) 4625–4665, https://doi.org/10.1039/
D0EE02620D.
[5] L. Shan, Y. Wang, S. Liang, B. Tang, Y. Yang, Z. Wang, B. Lu, J. Zhou, Interfacial
Declaration of Competing Interest
adsorption–insertion mechanism induced by phase boundary toward better
aqueous Zn-ion battery, InfoMat 3 (2021) 1028–1036.
The authors declare that they have no known competing financial [6] L.E. Blanc, D. Kundu, L.F. Nazar, Scientific challenges for the implementation of
interests or personal relationships that could have appeared to influence Zn-ion batteries, Joule. 4 (4) (2020) 771–799, https://doi.org/10.1016/j.
joule.2020.03.002.
the work reported in this paper. [7] S.H. Park, S.Y. Byeon, J.-H. Park, C. Kim, Insight into the Critical Role of Surface
Hydrophilicity for Dendrite-Free Zinc Metal Anodes, ACS Energy Lett. 6 (9) (2021)
3078–3085, https://doi.org/10.1021/acsenergylett.1c0152110.1021/
Acknowledgements acsenergylett.1c01521.s001.

This work was supported by the National Research Foundation of

8
J.-H. Park et al. Chemical Engineering Journal 433 (2022) 133532

[8] J. Wang, Y. Yang, Y. Zhang, Y. Li, R. Sun, Z. Wang, H. Wang, Strategies towards the [31] W. Deng, Z. Zhou, Y. Li, M. Zhang, X. Yuan, J. Hu, Z. Li, C. Li, R. Li, High-capacity
challenges of zinc metal anode in rechargeable aqueous zinc ion batteries, Energy layered magnesium vanadate with concentrated gel electrolyte toward high-
Storage Mater. 35 (2021) 19–46, https://doi.org/10.1016/j.ensm.2020.10.027. performance and wide-temperature Zinc-ion battery, ACS Nano. 14 (11) (2020)
[9] Q.-N. Zhu, Z.-Y. Wang, J.-W. Wang, X.-Y. Liu, D. Yang, L.-W. Cheng, M.-Y. Tang, Y. 15776–15785, https://doi.org/10.1021/acsnano.0c0683410.1021/
u. Qin, H. Wang, Challenges and strategies for ultrafast aqueous zinc-ion batteries, acsnano.0c06834.s001.
Rare Met. 40 (2) (2021) 309–328, https://doi.org/10.1007/s12598-020-01588-x. [32] J.S. Chae, S.K. Park, K.C. Roh, H.S. Park, Electrode materials for biomedical
[10] J. Gao, X. Xie, S. Liang, B. Lu, J. Xhou, Inorganic Colloidal Electrolyte for Highly patchable and implantable energy storage devices, Energy Storage Mater. 24
Robust Zinc-Ion Batteries, Nano-Micro Lett. 13 (2021) 69, https://doi.org/ (2020) 113–128, https://doi.org/10.1016/j.ensm.2019.04.032.
10.1007/s40820-021-00595-6. [33] J. Cong, X. Shen, Z. Wen, X. Wang, L. Peng, J. Zeng, J. Zhao, Ultra-stable and
[11] C. Li, X. Xie, H. Liu, P. Wang, C. Deng, B. Lu, J. Zhou, S. Liang, Integrated ‘all-in- highly reversible aqueous zinc metal anodes with high preferred orientation
one’ strategy to stabilize zinc anodes for high-performance zinc-ion batteries, Natl. deposition achieved by a polyanionic hydrogel electrolyte, Energy Storage Mater.
Sci. Rev. (2021), https://doi.org/10.1093/nsr/nwab177. 35 (2021) 586–594, https://doi.org/10.1016/j.ensm.2020.11.041.
[12] Z. Yi, G. Chen, F. Hou, L. Wang, J. Liang, Strategies for the stabilization of Zn metal [34] M. Zhu, J. Hu, Q. Lu, H. Dong, D.D. Karnaushenko, C. Becker, D. Karnaushenko,
anodes for Zn-ion batteries, Adv. Energy Mater. 11 (2021) 2003065. Y. Li, H. Tang, Z. Qu, J. Ge, O.G. Schmidt, A patternable and in situ formed
[13] J. Bae, Y. Li, F. Zhao, X. Zhou, Y. Ding, G. Yu, Designing 3D nanostructured garnet polymeric zinc blanket for a reversible zinc anode in a skin-mountable
frameworks for enhancing ionic conductivity and flexibility in composite polymer microbattery, Adv. Mater. 33 (8) (2021) 2007497, https://doi.org/10.1002/adma.
electrolytes for lithium batteries, Energy Storage Mater. 15 (2018) 46–52, https:// v33.810.1002/adma.202007497.
doi.org/10.1016/j.ensm.2018.03.016. [35] K. Leng, G. Li, J. Guo, X. Zhang, A. Wang, X. Liu, J. Luo, A safe polyzwitterionic
[14] J. Zhao, K.K. Sonigara, J. Li, J. Zhang, B. Chen, J. Zhang, S.S. Soni, X. Zhou, G. Cui, hydrogel electrolyte for long-life quasi-solid state zinc metal batteries, Adv. Funct.
L. Chen, A smart flexible zinc battery with cooling recovery ability, Angew. Chem. Mater. 30 (23) (2020) 2001317, https://doi.org/10.1002/adfm.v30.2310.1002/
Int. Ed. 56 (27) (2017) 7871–7875, https://doi.org/10.1002/anie.201704373. adfm.202001317.
[15] B. Xu, X. Li, C. Yang, Y. Li, N.S. Grundish, P.-H. Chien, K. Dong, I. Manke, R. Fang, [36] K.D. Fong, J. Self, K.M. Diederichsen, B.M. Wood, B.D. McCloskey, K.A. Persson,
N. Wu, H. Xu, A. Dolocan, J.B. Goodenough, Interfacial chemistry enables stable Ion transport and the true transference number in nonaqueous polyelectrolyte
cycling of all-solid-state Li metal batteries at high current densities, J. Am. Chem. solutions for lithium ion batteries, ACS Cent. Sci. 5 (7) (2019) 1250–1260, https://
Soc. 143 (17) (2021) 6542–6550, https://doi.org/10.1021/jacs.1c0075210.1021/ doi.org/10.1021/acscentsci.9b00406.
jacs.1c00752.s00110.1021/jacs.1c00752.s00210.1021/jacs.1c00752.s003. [37] J. Hao, B.o. Li, X. Li, X. Zeng, S. Zhang, F. Yang, S. Liu, D. Li, C. Wu, Z. Guo, An in-
[16] B. Pal, S. Yang, S. Ramesh, V. Thangadurai, R. Jose, Electrolyte selection for depth study of Zn metal surface chemistry for advanced aqueous Zn-ion batteries,
supercapacitive devices: a critical review, Nanoscale Adv. 1 (10) (2019) Adv. Mater. 32 (34) (2020) 2003021, https://doi.org/10.1002/adma.
3807–3835, https://doi.org/10.1039/C9NA00374F. v32.3410.1002/adma.202003021.
[17] J. Hao, X. Li, S. Zhang, F. Yang, X. Zeng, S. Zhang, G. Bo, C. Wang, Z. Guo, [38] F. Liu, J. Liu, Agarose based solid electrolyte for all-solid-state lithium ion batteries
Designing dendrite-free zinc anodes for advanced aqueous zinc batteries, Adv. working from -20 ◦ C to 80 ◦ C, J. Electrochem. Soc. 167 (8) (2020) 080519, https://
Funct. Mater. 30 (30) (2020) 2001263, https://doi.org/10.1002/adfm. doi.org/10.1149/1945-7111/ab8925.
v30.3010.1002/adfm.202001263. [39] Q.i. Yang, Q. Li, Z. Liu, D. Wang, Y. Guo, X. Li, Y. Tang, H. Li, B. Dong, C. Zhi,
[18] Z. Hou, H. Tan, Y. Gao, M. Li, Z. Lu, B. Zhang, Tailoring desolvation kinetics Dendrites in Zn-based batteries, Adv. Mater. 32 (48) (2020) 2001854, https://doi.
enables stable zinc metal anodes, J. Mater. Chem. A. 8 (37) (2020) 19367–19374, org/10.1002/adma.202001854.
https://doi.org/10.1039/D0TA06622B. [40] T. Wang, C. Li, X. Xie, B. Lu, Z. He, S. Liang, J. Zhou, Anode materials for aqueous
[19] J.-M. Kim, C. Kim, S. Yoo, J.-H. Kim, J.-H. Kim, J.-M. Lim, S. Park, S.-Y. Lee, zinc ion batteries: mechanisms, properties, and perspectives, ACS Nano. 14 (12)
Agarose-biofunctionalized, dual-electrospun heteronanofiber mats: toward metal- (2020) 16321–16347, https://doi.org/10.1021/acsnano.0c07041.
ion chelating battery separator membranes, J. Mater. Chem. A 3 (20) (2015) [41] R. Zhao, Y. Yang, G. Liu, R. Zhu, J. Huang, Z. Chen, Z. Gao, X. Chen, L. Qie,
10687–10692, https://doi.org/10.1039/C5TA02445E. Redirected Zn electrodeposition by an anti-corrosion elastic constraint for highly
[20] C. Kim, M. Ko, S. Yoo, S. Chae, S. Choi, E.-H. Lee, S. Ko, S.-Y. Lee, J. Cho, S. Park, reversible Zn anodes, Adv. Funct. Mater. 31 (2) (2021) 2001867, https://doi.org/
Novel design of ultra-fast Si anodes for Li-ion batteries: crystalline Si@amorphous 10.1002/adfm.202001867.
Si encapsulating hard carbon, Nanoscale 6 (18) (2014) 10604–10610, https://doi. [42] Y. Yang, C. Liu, Z. Lv, H. Yang, Y. Zhang, M. Ye, L. Chen, J. Zhao, C.C. Li,
org/10.1039/C4NR02394C. Synergistic manipulation of Zn2+ ion flux and desolvation effect enabled by anodic
[21] C. Kim, J.Y. Jang, N.-S. Choi, S. Park, Multi-functionalities of natural growth of a 3D ZnF2 matrix for long-lifespan and dendrite-free zn metal anodes,
polysaccharide for enhancing electrochemical performance of macroporous Si Adv. Mater. 33 (11) (2021) 2007388, https://doi.org/10.1002/adma.202007388.
anodes, RSC Adv. 4 (6) (2014) 3070–3074, https://doi.org/10.1039/C3RA45863F. [43] Z. Li, L. Wu, S. Dong, T. Xu, S. Li, Y. An, J. Jiang, X. Zhang, Pencil drawing stable
[22] H. Tabani, S. Asadi, S. Nojavan, M. Parsa, Introduction of agarose gel as a green interface for reversible and durable aqueous zinc-ion batteries, Adv. Funct. Mater.
membrane in electromembrane extraction: an efficient procedure for the extraction 31 (4) (2021) 2006495, https://doi.org/10.1002/adfm.202006495.
of basic drugs with a wide range of polarities, J. Chromatogr. A. 1497 (2017) [44] Z. Zhao, J. Zhao, Z. Hu, J. Li, J. Li, Y. Zhang, C. Wang, G. Cui, Long-life and deeply
47–55, https://doi.org/10.1016/j.chroma.2017.03.075. rechargeable aqueous zn anodes enabled by a multifunctional brightener-inspired
[23] H.-J. Koo, S.T. Chang, J.M. Slocik, R.R. Naik, O.D. Velev, Aqueous soft matter interphase, Energy Environ. Sci. 12 (6) (2019) 1938–1949, https://doi.org/
based photovoltaic devices, J. Mater. Chem. 21 (1) (2011) 72–79, https://doi.org/ 10.1039/C9EE00596J.
10.1039/C0JM01820A. [45] M. Zhou, S. Guo, J. Li, X. Luo, Z. Liu, T. Zhang, X. Cao, M. Long, B. Lu, A. Pan,
[24] W.G. Moon, G.-P. Kim, M. Lee, H.D. Song, J. Yi, A biodegradable gel electrolyte for G. Fang, J. Zhou, S. Liang, Surface-preferred crystal plane for a stable and
use in high-performance flexible supercapacitors, ACS Appl. Mater. Interfaces. 7 reversible zinc anode, Adv. Mater. 33 (21) (2021) 2100187, https://doi.org/
(6) (2015) 3503–3511, https://doi.org/10.1021/am5070987. 10.1002/adma.202100187.
[25] D.S. Franklin, S. Guhanathan, Synthesis and characterization of citric acid-based [46] H. Qiu, X. Du, J. Zhao, Y. Wang, J. Ju, Z. Chen, Z. Hu, D. Yan, X. Zhou, G. Cui, Zinc
ph-sensitive biopolymeric hydrogels, Polym. Bull. 71 (1) (2014) 93–110, https:// anode-compatible in-situ solid electrolyte interphase via cation solvation
doi.org/10.1007/s00289-013-1047-4. modulation, Nat. Commun. 10 (2019) 5374, https://doi.org/10.1038/s41467-019-
[26] F. Yu, H. Zhang, L. Zhao, Z. Sun, Y. Li, Y. Mo, Y. Chen, A flexible cellulose/ 13436-3.
methylcellulose gel polymer electrolyte endowing superior Li+ conducting [47] J. Huang, X. Chi, Q.i. Han, Y. Liu, Y. Du, J. Yang, Y.u. Liu, Thickening and
property for lithium ion battery, Carbohydr. Polym. 246 (2020) 116622, https:// homogenizing aqueous electrolyte towards highly efficient and stable Zn metal
doi.org/10.1016/j.carbpol.2020.116622. batteries, J. Electrochem. Soc. 166 (6) (2019) A1211–A1216, https://doi.org/
[27] R.F.M.S. Marcondes, P.S. D’Agostini, J. Ferreira, E.M. Girotto, A. Pawlicka, D. 10.1149/2.1031906jes.
C. Dragunski, Amylopectin-rich starch plasticized with glycerol for polymer [48] K.E.K. Sun, T.K.A. Hoang, T.N.L. Doan, Y. Yu, X. Zhu, Y. Tian, P. Chen, Suppression
electrolyte application, Solid State Ion. 181 (13-14) (2010) 586–591, https://doi. of dendrite formation and corrosion on zinc anode of secondary aqueous batteries,
org/10.1016/j.ssi.2010.03.016. ACS Appl. Mater. Interfaces. 9 (2017) 9681-9687. https://doi.org/10.1021/
[28] W. Guo, Z. Cong, Z. Guo, C. Chang, X. Liang, Y. Liu, W. Hu, X. Pu, Dendrite-free Zn acsami.6b16560.
anode with dual channel 3D porous frameworks for rechargeable Zn batteries, [49] C. Xie, Y. Li, Q. Wang, D. Sun, Y. Tang, H. Wang, Issues and solutions toward zinc
Energy Storage Mater. 30 (2020) 104–112, https://doi.org/10.1016/j. anode in aqueous zinc-ion batteries: A mini review, Carbon Energy. 2 (2020) 540-
ensm.2020.04.038. 560. https://doi.org/10.1002/cey2.67.
[29] F. Mo, Z. Chen, G. Liang, D. Wang, Y. Zhao, H. Li, B. Dong, C. Zhi, Zwitterionic [50] J. Jeong, H.-C. Shin, In-depth analysis of coulombic efficiency of zinc-air secondary
sulfobetaine hydrogel electrolyte building separated positive/neegative ion batteries, J. Electrochem. Sci. Technol. 11 (2020) 26–32.
migration channels for aqueous Zn-MnO2 batteries with superior rate capabilities, [51] M. Fayette, H.J. Chang, I.A. Rodriguez-Perez, X. Li, D. Reed, Electrodeposited zinc-
Adv. Energy Mater. 10 (2020) 2000035, https://doi.org/10.1002/ based films as anodes for aqueous zinc, ACS Appl. Mater. Interfaces. 12 (2020)
aenm.202100798. 42763–42772, https://doi.org/10.1021/acsami.0c10956.
[30] M. Chen, J. Chen, W. Zhou, X. Han, Y. Yao, C.-P. Wong, Realizing an all-round [52] D. Chao, W. Zhou, F. Xie, C. Ye, H. Li, M. Jaroniec, S.-Z. Qiao, Roadmap for
hydrogel electrolyte toward environmentally adaptive dendrite-free aqueous advanced aqueous batteries: from design of materials to applications, Sci. Adv. 6
Zn–MnO2 batteries, Adv. Mater. 33 (9) (2021) 2007559, https://doi.org/10.1002/ (2020) eaba4098, https://doi.org/10.1126/sciadv.aba4098.
adma.v33.910.1002/adma.202007559.