Nano Energy 62 (2019) 550–587

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

Review

Advanced rechargeable zinc-based batteries: Recent progress and future T

perspectives
Hongfei Lia,b,1, Longtao Mab,1, Cuiping Hanc, Zifeng Wangb, Zhuoxin Liub, Zijie Tangb,
Chunyi Zhib,d,∗
a
Songshan Lake Materials Laboratory, Dongguan, Guangdong, 523808, China
b
Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China
c
College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518000, China
d
Shenzhen Research Institute, City University of Hong Kong, High-Tech Zone, Nanshan District, Shenzhen, 518057, China

ARTICLE INFO ABSTRACT

Keywords: Featuring with low cost, exceptional inherent safety and decent electrochemical performance, rechargeable Zn-
Zinc-based batteries based batteries (RZBs) have attracted increased attention and revived research efforts recently as a compelling
Zinc ion intercalation alternative battery chemistry to Li-ion. However, some challenges still stand in the way of the development of
Zinc ion batteries these energy storage systems, such as low operation voltage, instability of cathode materials as well as dis-
Post Li-Ion batteries
solution of Zn electrode, etc. In this review, we present a comprehensive overview of recent progress in different
Aqueous batteries
RZBs systems including mild electrolyte RZBs, alkaline RZBs, hybrid RZBs, Zn-ion capacitors and Zn air batteries.
Flexible energy storage
The fundamental chemistry of various RZB systems, different cathode materials, optimization of Zn anode as
well as various types of electrolytes and their influence on the battery performance are summarized. The major
issues of different components along with respective strategies to alleviate them are discussed, aiming at pro-
viding a general guide for design and construction of high-performance RZBs. Additionally, the development of
RZBs with different features in the last few years are summarized. Finally, we discuss the limitations and
challenges that need to be overcome, providing potential future research directions in the field of next-gen-
eration RZBs.

1. Introduction energetic batteries generally provide limited power, whereas super-

The growing demand for green and sustainable energy storage for
various applications, such as portable and flexible electronics and grid-
scale energy storage systems, has stimulated the development of ad-
vanced energy storage technologies. Currently, Li-ion batteries have
dominated the secondary battery applications ranging from portable
electronic gadgets (mobile phones and smart watches, etc.) to auto-
motive vehicles due to their high energy density and mature manu-
facturing technology [1]. However, the long-term concerns of high cost,
limited reserves of lithium, and safety issues of Li-ion batteries have
driven the researchers to search for alternative energy storage solutions
for some specific application scenarios [2]. Low-cost aqueous batteries
employing multivalent charge carrier Zn2+, Mg2+, Ca2+ and Al3+ are
highly desirable, as the intercalation chemistry of divalent cations in-
volves in redox reactions.
Among various electrochemical systems, it is well known that
capacitors provide low energy. Lithium ion batteries (LIBs) may deliver
both high power and energy density, but the safety and environmental
issues cannot be neglected. RZBs have drawn particular attention due to
the following advantages of metallic zinc: (1) high theoretical capacity
(820 mA h g−1 or 5854 mA h cm−3), as well as balanced kinetics, sta-
bility and reversibility in aqueous solutions (Fig. 1 and Table 1); (2) low
electrochemical potential (−0.763 V versus the standard hydrogen
electrode (SHE)) and two-electron transfer during redox reaction
leading to a high energy density; (3) high natural abundance and mass
production; (4) low toxicity and intrinsic safety from their aqueous
nature [3,4].
The investigation of Zn as anode material can date back to the
Voltaic pile, the very first electrochemical battery which was invented
by Alessandro Volta in the late nineteenth century [6]. Since then, zinc
has found applications in several other types of batteries including
Zn–air, alkaline Zn–MnO2, Zn–NiOOH and Zn–Ag2O, which have been

∗
Corresponding author. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China.
E-mail address: cy.zhi@cityu.edu.hk (C. Zhi).
1
These authors contribute equally to this work.

https://doi.org/10.1016/j.nanoen.2019.05.059
Received 6 April 2019; Received in revised form 19 May 2019; Accepted 20 May 2019
Available online 23 May 2019
2211-2855/ © 2019 Elsevier Ltd. All rights reserved.
H. Li, et al. Nano Energy 62 (2019) 550–587

rechargeable batteries using mild aqueous electrolytes [18]. Lu et al.

published a research news that briefly summarized the recent advances
in flexible ZIBs from the perspective of flexibility design [19]. However,
these reviews mainly focused on the RZBs that operated in neutral pH
(or slightly acidic) electrolytes and didn't involve the alkaline RZBs
(such as Zn–Ni, Zn–Co alkaline batteries), Zn ion hybrid capacitors, and
Zn air batteries which also play an important role in the research area of
RZBs.
In this manuscript, we present a comprehensive review on the re-
cent development of various rechargeable Zn batteries including mild
electrolyte RZBs, alkaline RZBs, hybrid RZBs, Zn ion capacitors, and Zn
air batteries with an emphasis on: (1) reaction mechanisms of different
Zn-based battery systems that operated in different electrolytes (mild,
alkaline, hydrogel and ionic liquid electrolytes); (2) a wide range of
cathode materials for RZBs based on different mechanisms; (3) funda-
mental electrochemistry of Zn electrode as well as strategies for im-
proving the Zn anode performance; (4) various electrolytes including
neutral, alkaline, hydrogel and ionic liquid electrolytes and their in-
Fig. 1. Zinc property regimes. Note that Mg, Si, Ti and Fe cannot be reversibly fluence on the RZB performance. In addition, the development of
stripped/plated from aqueous media, Cd and Pb have low specific energy flexible RZBs with different features and multiple functionalities in the
density and high toxicity, while Li, Na, K and Ca are neither stable nor re- last few years are also summarized. Finally, the challenges and poten-
versible in aqueous solutions [5]. Although Al has larger capacities, it cannot be
tial future research directions in the field of next-generation RZBs are
electrochemically deposited in a conventional aqueous solution due to its lower
discussed. We hope this review can serve as a comprehensive reference
standard electrode potential of Al3+/Al (−1.68 V). Compare with other metals,
that attract more researchers to carrying out impactful research on
Zn shows balanced kinetics, high stability in aqueous solutions. More im-
portantly, Zn can be easily stripped/plated from aqueous media, which is fa- RZBs and facilitate their further development.
vorable for aqueous energy storage systems.
2. Mechanisms of rechargeable Zn-based batteries
Table 1
The reaction mechanisms of RZBs are different from the well-es-
A comparison of monovalent/multivalent metals in the standard potential,
theoretical capacity, and ionic radius [3]. tablished lithium/sodium-ion-based energy storage chemistries (such as
insertion, conversion, and alloying reaction mechanism), which remain
Metal Potential Ionic Hydrated Specific Specific controversial and are under debate. So far, seven different reaction
electrode vs SHE (V) radius ion radius gravimetric volumetric
(Å) (Å) capacity (mAh capacity
mechanisms have been proposed for RZBs, which includes: (1) Zn2+
g−1) (mAh cm−3) intercalation/deintercalation mechanism, (2) co-insertion mechanism,
(3) conversion reaction mechanism, (4) hybrid chemistry mechanism,
Li −3.04 0.76 3.40–3.82 3860 2061 (5) charge-state change of electroactive groups, (6) protonation/de-
Na −2.713 1.02 2.76–3.60 1166 1129
K −2.924 1.38 2.01–3.31 685 610
protonation mechanism, and (7) Zn-air mechanism.
Mg −2.356 0.72 3.00–4.70 2206 3834
Ca −2.84 1.00 4.12–4.20 1337 2072 2.1. Zn2+ intercalation−deintercalation mechanism
Al −1.676 0.53 4.80 2980 8046
Zn −0.763 0.75 4.12–4.30 820 5855
Zn2+ has a relatively small ionic radius (0.75 Å) and the size of
hydrated Zn2+ is also comparable with hydrated Li+ (Table 1), which is
beneficial for the intercalation/deintercalation of divalent Zn2+ ions
successfully commercialized and most of them are still in use today, as into/from the crystal structures of cathode materials. Generally, RZBs
illustrated in Fig. 2. Nowadays, one-third of the world battery market is that consist of a neutral Zn2+-containing electrolyte, a cathode for
composed by zinc-based battery systems, which highlights its im- hosting Zn2+ and a zinc electrode are called zinc-ion batteries (ZIBs),
portance as power sources for a wide range of applications. In 1986, which have attracted particular interests in the recent years [20]. So
Yamamoto and co-workers investigated the Zn–MnO2 battery systems far, different kinds of transition metal oxides and compounds with a
that operated in a mild ZnSO4 electrolyte for the first time [7]. How- two-dimensional (2D) layered structure or tunnel-type structure that
ever, the operation mechanism of this novel aqueous battery was not enable the reversible insertion/extraction of Zn2+ into/from the lattice
clearly revealed. In 2011, Kang and co-workers firstly proposed the have been investigated. For example, by using in situ X-ray absorption
concept of “Zn-ion battery” (ZIB), in which a reversible Zn2+ insertion/ near edge structure (XANES) and in situ synchrotron X-ray diffraction
extraction into/from MnO2 was reported [8]. Since then, extensive ef- (XRD) techniques, Kim and co-workers elucidated that inter-
forts have been devoted to developing various ZIB systems that operate calation−deintercalation mechanism of Zn2+ into/from the orthor-
in an aqueous neutral or mildly acidic electrolytes, including Zn-Prus- hombic tunnel-type γ-MnO2 (Fig. 3) [21]. During the discharge process
sian blue analogues (PBA), Zn-vanadium (V)-based, Zn- molybdenum (corresponding to Zn2+ intercalation), the initial tunnel-type γ-MnO2
(Mo)-based, and Zn-Quinone batteries. These advances contribute a lot phase is successively transformed to spinel-type ZnMn2O4, tunnel-type
to the revival of RZBs for building highly reversible, and sustaining γ-ZnxMnO2, and layered-type L-ZnyMnO2, which is accompanied by the
long-life power sources, which offer compelling alternatives to Li-ion reduction of MnO2 from Mn4+ to the Mn3+ and Mn2+, respectively.
and open new opportunities for next-generation energy-storage tech- Upon charging (Zn2+ deintercalation), these Zn-inserted manganese
nologies. phases gradually revert back to the original state of γ-MnO2, revealing a
The promising development of RZBs has attracted increasing in- reversible Zn2+ insertion/extraction mechanism for γ-MnO2.
terest and a few review papers have been reported in the last two years. In addition to manganese-based oxides, other materials such as
For example, Fan et al. [3], Liang et al. [15], Alshareef et al. [16], and vanadium-based compounds have been investigated to be the electro-
Myung et al. [17] summarized recent advances of aqueous Zn batteries active hosts for reversible Zn2+ intercalation−deintercalation. Mai and
with mild electrolytes. Wang and co-workers reviewed various co-workers demonstrated a reversible Zn2+ ion (de)intercalation

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H. Li, et al.
Fig. 2. Timeline of the development history for different kinds of zinc-based batteries [8–14].
storage process in layered Na0.33V2O5 nanowire by using XRD, X-ray
photoelectron spectroscopy (XPS), field emission scanning electron
microcopy (FESEM), and transmission electron microcopy (TEM) [22].
As shown in Fig. 4, during the discharge process, a new ZnxNa0.33V2O5
phase appeared which is probably related to the crystal distortion be-
cause of Zn2+ intercalation. In contrast, this new phase gradually dis-
appears due to Zn2+ deintercalation when the battery is charging to
1.6 V, indicating that such phase transformation and structural varia-
tion of Na0.33V2O5 is highly reversible.
2.2. Co-insertion mechanism
Recently, the reversible co-insertion of ions (H+ and Zn2+) and/or
molecules (H2O) into host materials of RZBs have been demonstrated
through electrochemical and structural analysis. Wang et al. first pro-
posed a H+ and Zn2+ co-insertion reaction mechanism for RZBs based
on Akhtenskite-type MnO2 [23].
Discharge galvanostatic intermittent titration technique (GITT),
discharge curves and XRD tests verified that the first discharge platform
(Region I) and the second discharge platform (Region II) are attributed
to the intercalation of H+ and Zn2+, respectively (Fig. 5a). This me-
chanism was further confirmed by the electrochemical behavior com-
parison of Akhtenskite MnO2 in electrolytes without H+ or Zn2+
(Fig. 5b and c). Region I or II was significantly influenced by elim-
inating H+ or Zn2+, respectively, which was reasonable to postulate
that both H+ and Zn2+ had participated in the charge/discharge pro-
cess. Furthermore, both MnOOH and ZnMn2O4 (from Zn2+ intercala-
tion) phases were observed in succession during the discharge process
(Fig. 5d), which strongly support the consequent H+ and Zn2+ co-in-
sertion mechanism for Akhtenskite MnO2.
Zn2+ and water co-intercalation reaction mechanism has been stu-
died recently by Wang and co-workers for aqueous Zn/V2O5 battery
[10]. Combined studies of electrochemical tests, XRD, TEM, and XPS
revealed that the initial layered V2O5 gradually evolved into a layered
ZnxV2O5·nH2O phase during the discharge process and its interlayer
spacing expanded from 4.4 to 13.4 Å, which can be attributed to the co-
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Nano Energy 62 (2019) 550–587
insertion of hydrated Zn2+ and H2O molecule. The subsequent charging
process showed the reverse structural evolution of discharging, which is
associated with the extraction of hydrated Zn2+ from the host lattice.
The reaction mechanism of the Zn/V2O5 battery is schematically illu-
strated in Fig. 5e and the equation can be expressed as follows:
V2O5 + xZn2+ + 2xe− + nH2O ↔ ZnxV2O5·nH2O (1)
2+
where x denotes the number of reversibly inserted Zn . The co-in-
tercalated water can effectively shield the electrostatic interactions
between Zn2+ ions and the crystal structure of host material. This
charge-shielding function can be evidenced by the fact that only very
limited capacity can be delivered in organic electrolyte (Zn(CF3SO3)2 in
acetonitrile) due to the absence of H2O.
2.3. Conversion reaction
Different from the traditional Zn2+ insertion/extraction chemistry,
Liu and co-workers presented a reversible conversion reaction me-
chanism in aqueous Zn/MnO2 systems, which operates based on the
conversion reaction between protons and MnO2 (Fig. 6a–g) [24]. When
discharging, α-MnO2 reacts with proton (H+) to form a new MnOOH
phase at the fully discharged state (MnO2 + H+ + e− ↔ MnOOH).
Then, the sequent OH− ion will further react with ZnSO4 and H2O in
the electrolyte to form a kind of zinc hydroxide sulfate hydrates
(ZnSO4[Zn(OH)2]3·xH2O) to reach a charge balance in the electrolyte
system. This reaction mechanism was evidenced by combined studies of
TEM, XRD and STEM-EDS mapping. After discharging, the initial well-
defined α-MnO2 evolved to short nanorods and nanoparticle aggregates
with lattice distances of 0.33 and 0.26 nm, respectively, which were
further identified to MOOH phase by ex situ XRD, rather than ZnxMnO2
or ZnMn2O4. STEM-EDS mapping of the α-MnO2 electrode in the dis-
charged state during the first cycle showed that the short nanorods and
nanoparticles consist of O and Mn elements, while Zn is mainly dis-
tributed on the flakelike substance (ZnSO4[Zn(OH)2]3·xH2O), further
confirming the conversion reaction mentioned above.
H. Li, et al.
Fig. 3. Schematic diagram of Zn2+-intercalation mechanism in γ-MnO2. Reproduced with permission [21]. Copyright 2015, American Chemical Society.
Recently, the conversion reaction mechanism for flower-like Mn3O4
has been investigated by Liang and co-workers [25]. The ex situ XRD,
SEM and XPS results of the Mn3O4 electrode at full discharge/charge
states showed that the MnO phase and ZnSO4[Zn(OH)2]3·5H2O phase
appear at the first full discharge state (Fig. 6h), which is due to the fact
that Mn3+ in Mn3O4 electrode was reduced to Mn2+ and exists in the
form of MnO. Meanwhile, ZnSO4[Zn(OH)2]3·5H2O phase was clearly
observed in the XRD and SEM image of the Mn3O4 electrode at the first
discharge state, due to the reaction of ZnSO4 and H2O and OH− ions.
(Fig. 6i). Elemental mapping images shows that Mn, O and Zn elements
are homogeneously distributed along the conductive substrate at the
first discharge of 1.0 V, which is in accordance with the XRD results
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Nano Energy 62 (2019) 550–587
(Fig. 6j).
2.4. Hybrid chemistry mechanism
More recently, hybrid design via coupling a lithium or sodium
based-intercalation cathode with a metallic Zn anode was introduced in
RZBs, representing a new class of aqueous energy storage systems, such
as LiMn2O4//Zn, LiFePO4//Zn, and Na3V2(PO4)3@C//Zn [26]. Dif-
ferent from the traditional “intercalation−deintercalation” type bat-
teries, these hybrid batteries operate based on two different electro-
chemical processes: Zn deposition-dissolution in anode and Li+ or Na+
-induced oxidization/reduction in cathode, as shown in Fig. 7a. The
H. Li, et al.
Fig. 4. (a) Ex situ XRD patterns of Na0.33V2O5 at various charge/discharge steps, and (b) corresponding charge and discharge curves at 200 mA g−1. (c) Schematic
diagram of the Zn2+-intercalation mechanism in Na0.33V2O5. (d) TEM and (e) TEM-Energy Dispersive X-ray spectroscopy (EDS) element mapping images of
Na0.33V2O5 shows the elemental distributions of Zn, Na, V and O in Na0.33V2O5 after 3 cycles (f) The selected area electron diffraction (SAED) pattern and g) HRTEM
image of Na0.33V2O5 after 100 cycles. Reproduced with permission [22]. Copyright 2018, Wiley-VCH.
electrolyte here acts as conducting ions and cooperates with the elec-
trodes to store energy, rather than used as the simple supporting media
in “rocking chair” type batteries. These hybrid energy storage systems
significantly enrich the existing rechargeable battery chemistry and
open new research era for high-performance RZB design.
Taking LiMn2O4//Zn battery as an example, a mixed aqueous so-
lution of LiCl and ZnCl2 was employed as electrolyte [27]. The hybrid
reaction mechanism can be exemplified by XRD results of spinal
LiMn2O4 and Zn anode at different charge/discharge depths, as shown
in Fig. 7b and c. Upon charging, characteristic peaks of (111), (311) and
(400) planes of LiMn2O4 shifted toward higher angles, indicating the
extraction of Li+ ions and the formation of Mn2O4 [28]; During the
discharging process, these characteristic peaks of the spinal LiMn2O4
shifted negatively to their original positions, reflecting a reversible Li+
intercalation/deintercalation for LiMn2O4 cathode. The reversible de-
position/dissolution mechanism of Zn anode on a stainless-steel current
collector upon cycling was also confirmed by XRD data (Fig. 7c). Before
charging, only characteristic peaks of the stainless-steel current col-
lector can be observed. After charging, characteristic peaks of (002),
(010) and (011) planes of zinc were clearly detected, suggesting that
Zn2+ ions in the hybrid electrolyte were deposited on the stainless-steel
current collector.
The electrochemical reaction between the LiMn2O4 cathode and Zn
anode can be expressed as follows:
Cathode: LiMn2O4 ↔ Li1-xMn2O4 + xLi+ + xe-
Anode: Zn2+ + x2e- ↔ xZn
+
In which the reversible Li ion intercalation/deintercalation pro-
cess occurs at the cathode part, while the reversible Zn deposition/
dissolution takes place in anode part.
2.5. Charge-state change of electroactive groups
Recently, a series of organic compounds have been explored as
cathodes for high-performance and rechargeable zinc-ion batteries,
including calix quinone, tetrachloro-1, p-chloranil and so on [29,30].
The redox mechanism of electrochemically reactive electron carbonyl
compounds can be explained by the charge-state change of
Nano Energy 62 (2019) 550–587
electroactive groups. To analyze the exact sites of Zn ion uptake, Zhao
et al. utilized the electrostatic potential (ESP) approach, which is often
applied to deduce the electrophilic or nucleophilic reaction in organic
chemistry, to deduce the active sites of organic electrodes. The sites
with more negative ESP are attractive for discharge reaction as it in-
volves Zn2+ uptake [29]. As shown in Fig. 8E, for the C4Q molecular
structure, the carbonyls on and under a molecule show lower ESP than
the bilateral carbonyls. In other words, these carbonyl groups are more
favorable for Zn2+ adsorption.
Different with inorganic materials, organic materials usually have
intrinsically low crystallinity, which is difficult to be accurately char-
acterized with traditional approaches such as XRD and TEM. Zhao et al.
employed in situ technologies of attenuated total reflection–Fourier
transform IR (ATR-FTIR) spectroscopy, Raman spectroscopy, and ul-
traviolet–visible (UV–vis) spectroscopy to monitor the reaction me-
chanism of C4Q electrodes in RZBs. During the discharging process, two
carbonyl group at the top of the C4Q molecule will accept two electrons
together with one Zn2+ ion and two extra Zn2+ ions will be co-
ordinated with four carbonyls at the bottom of C4Q. Upon charging,
C4Q will be oxidized and hence the captured electrons and Zn2+ ions
will be released during the reverse charging process (Fig. 4F). The
electrochemical reaction Zn2+ uptake in C4Q can be expressed as fol-
lows:
C4Q + Zn2+ Zn3 C4Q (4)
(2)
(3) 2.6. Protonation/deprotonation mechanism
In addition to mild RZBs, alkaline RZBs batteries based on the
protonation/deprotonation mechanism such as Ni–Zn, Co–Zn batteries
have been considered as promising energy storage sources due to their
higher operation voltage (around 1.7–1.8 V) and higher energy density
compared with other aqueous rechargeable batteries.
In alkaline electrolyte, Ni or Co based oxide/hydroxide, sulfide, and
phosphide materials can react with OH− [31]. These transition metal
compounds store charges by a deprotonation/protonation mechanism
with the reaction of OH− in the electrolyte, which can be described as:
A(OH)2 + OH− ↔ AOOH + H2O + e− (5)
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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 5. (a) GITT profiles of akhtenskite-MnO2 electrode. (b) Charge and discharge curves of Akhtenskite MnO2with or without water. (c) Charge and discharge curves
of Akhtenskite MnO2with or without ZnSO4. (d) XRD patterns of Akhtenskite MnO2 when discharged to 1.3 and 1.0 V, respectively. Reproduced with permission
[23]. Copyright 2017, American Chemical Society. (e) Scheme illustration showing the reversible H2O and Zn2+ intercalation/deintercalation process into/from
ZnxV2O5·nH2O upon discharge. Reproduced with permission [10]. Copyright 2016, Springer Nature.

Where A represents for the transition metal cations such as Ni or Co.
For Co(OH)2, the reaction mechanism is slightly different from that of
Ni(OH)2. The product CoOOH could further transform to CoO2 during
the charging process [32]. Upon discharging, CoO2 was reduced to
Co3O4 reversibly. The two-steps reaction mechanism of Co3O4 can be
described as follows:
Co3O4 + OH- + H2O ↔ 3CoOOH + e−
3CoOOH +3OH- ↔ 3CoO2 + 3H2O + 3e-
As for Ni(OH)2 cathode, there are two main crystal structures: α-Ni
(OH)2 and β-Ni(OH)2. The β-Ni(OH)2 with well-ordered brucite-like
structure usually represents more stable phase with a theoretical ca-
pacity of 289 mAh g−1 and can be fabricated easily, therefore has been
the firstly used as cathode material for alkaline Ni–Zn battery [33].
However, the low electrical conductivity and metastable crystal struc-
ture of β-Ni(OH)2 usually result in low mass capacity and poor cycle
lifetime. In contrast, α-Ni(OH)2 generally verities predominant elec-
trochemical performance than β-Ni(OH)2 due to their hydrotalcite-like
and interesting interlayer structure with hydroxyl-deficient Ni(OH)2-x
layers intercalated by anions. The intercalation of anions gives rise to
larger interlayer spacing (> 7.0 Å) than that of β-Ni(OH)2 (4.6 Å),
(6)
which contribute to much higher electrochemical active site. Notably,
(7) the α-Ni(OH)2 is usually structurally vulnerable and can easily con-
verted to β-Ni(OH)2 in alkaline electrolyte.
Apart from transition metal oxide/hydroxide, Ni or Co based sul-
fides are also applied in alkaline RZBs due to their higher electrical
conductivity, enhanced electrochemical activity compared to their
metal oxides [34]. The transition metal sulfides show similar electro-
chemical behaviors through reversible surface redox reactions with

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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 6. (a–c) TEM/HRTEM images of α-MnO2 electrode discharged to 1 V (a–c) at the discharged state; (e–g) TEM/HRTEM images of α-MnO2 electrode charged back
to 1.8 V; (d) STEM-HAADF image and STEM–EDS mapping images for the MnO2 electrode at the discharged state in the first cycle. Reproduced with permission [24].
Copyright 2016, Springer Nature. (h) Ex situ XRD patterns of Mn3O4 electrode. (i) SEM images of Mn3O4 electrode when discharged to 1.0 V. (j) Elemental mapping
for Mn3O4 electrode when discharged to 1.0 V. Reproduced with permission [25]. Copyright 2018, Royal Society of Chemistry.

Fig. 7. (a) Schematic illustration of hybrid chemistry mechanism. (b) in-situ XRD measurement of LiMn2O4 cathode in LiMn2O4//Zn battery during the first cycle.
Characteristic peaks of (111), (311) and (400) planes shift reversibly, reflecting a reversible Li+ intercalation/deintercalation process for LiMn2O4 cathode. (c) ex-situ
XRD patterns of Zn on the stainless-steel current collector before (the down line) and after (the up line) charging, asterisk denotes the positions for the XRD patterns
of the stainless steel. After charging, characteristic peaks of (002), (010) and (011) planes of zinc were clearly detected. Reproduced with permission [27]. Copyright
2012, Elsevier.

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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 8. (a–e) The electrostatic potential (ESP)- mapped molecular van der Waals surface of typical quinone molecules. Surface local minima of ESP are represented as
blue spheres, and the corresponding ESP values are marked out by numbers. (f) Optimized configurations of calix [4] quinone (C4Q) before and after Zn2+ uptake.
Bottom: Corresponding configurations at different viewpoints. The distance between O–O and Zn–O has been labeled in angstroms [29]. Copyright 2018, American
Association.

OH−. The reaction of transition metal sulfides in alkaline RZBs can be

described as following:

AS + OH− ↔ ASOH + e− (8)

Where A stands for the transition metal cations.

Based on the aforementioned reaction mechanism, Lu and co-
workers reported an ultrathin nickel cobaltite (NiCo2O4) nanosheets
with enriched oxygen vacancies and surface phosphate ions
(P–NiCo2O4-x) for RZBs [35]. During the charging process, NiCo2O4 is
transformed into NiOOH and CoO2 after reacting with OH−. Mean-
while, [Zn(OH)4]2- is reduced into Zn by releasing OH− into the elec-
trolyte. Upon discharging, NiOOH and CoO2 was reduced to their
oxides with lower valence and Zn reacts with OH− anions from the
electrolyte to form the [Zn(OH)4]2- complex at the meantime. The re-
versible reaction mechanism of Zn–NiCo2O4 batteries can be expressed
as follows:

Cathode: NiCo2O4 + OH− + H2O ↔ NiOOH + 2CoOOH + e− (9)

Fig. 9. Basic structure and operation principle for a zinc–air battery.
CoOOH + OH− ↔ CoO2 + H2O + e− (10)

Anode: Zn(OH)42- + 2e- ↔ Zn + 4OH- (11) (e.g., concentrated KOH). Upon discharging, zinc reacts with OH− and
forms soluble zincate ions (Zn(OH)42−). As this process proceeds, these
3Zn(OH)42- + 2NiCo2O4↔2 NiOOH+ 4CoO2+ 6OH- + 2H2O +3Zn.
zincate ions become supersaturated in the electrolyte and subsequently
(12)
decompose to insoluble zinc oxide [37].
At the positive air cathode, O2 from the surrounding atmosphere
diffuses into the porous gas diffusion electrode (GDE) and the oxygen
2.7. Zn-air chemistry reduction reaction (ORR) then takes place at the air electrode of zin-
c–air batteries. The generated OH− ions migrate from the air cathode to
Zinc–air is an old and mature battery technology but has gained the Zn anode and complete the battery reaction. The general electro-
revived attention recently. With excellent reliability, high achievable chemical reaction process of zinc–air batteries can be summarized as
energy density and great safety, zinc–air batteries represent a powerful follows:
alternative to lithium-ion batteries for next generation of vehicle elec-
Anode: Zn + 4OH- ↔ Zn(OH)42- + 2e- (13)
trification and portable/wearable electronic devices [36]. Fig. 9 illus-
trates the basic structure and operation principle for a typical zinc–air Zn(OH)42- ↔ ZnO + H2O + 2OH -
(14)
battery. It usually consists of a negative zinc anode, a membrane se-
- -
parator and a positive air cathode as well as an alkaline electrolyte Cathode: O2 + 2H2O + 4e → 4OH (15)

557
H. Li, et al.
Fig. 10. Operating voltage versus specific capacity of various cathode materials for RZBs.
Overall reaction: 2Zn + O2 → 2ZnO (16)
3. Cathode materials for rechargeable Zn based batteries
Various kinds of cathode materials for RZBs have been developed
based on different reaction mechanisms, which mainly includes: (1)
manganese (Mn) based compounds; (2) vanadium (V) based com-
pounds; (3) Prussian blue analogs; (4) Li+ or Na+ ion-intercalated
materials; (5) Nickel (Ni) or cobalt (Co)-based materials; (6) organic
materials; (7) bifunctional air electrode materials for RZBs. The features
of these species, such as energy storage mechanism, testing voltage,
operating voltage, specific discharge capacity, and electrolyte used in
aqueous RZB systems, are summarized in Fig. 10 and Table 2. Besides,
the advantages and issues as well as the related improvement strategies
of these materials will be also discussed in this part.
3.1. Mn based cathode materials
As a typical transition metal element, manganese exists several
stable oxides (MnO, Mn3O4, Mn2O3, MnO2) and crystallizes in a re-
markable diversity of crystal structures and multivalent phases due to
different valence states of Mn: Mn2+, Mn3+, Mn4+, and Mn7+ [87].
With a wide variety of atomic architectures, phases, morphology and
porosity, manganese oxides exhibit different electrochemical behaviors
and various impressive electrochemical properties. In the past several
years, Mn-based materials have attracted incremental attention and
diverse manganese compounds have been explored for cathode mate-
rials of RZBs (Fig. 11), including α-MnO2 [8,88,89], β-MnO2 [39,40], γ-
MnO2 [39], δ-MnO2 [41], Akhtenskite-type MnO2 [23], Mn2O3 [43],
Mn3O4 [25,44] and ZnMn2O4 [22]. Among various manganese oxides,
α-MnO2 with (2 × 2) + (1 × 1) tunnels and γ-MnO2 with
(1 × 2) + (1 × 1) tunnel structure are the most widely investigated
phases and deliver high specific capacity (around 200–300 mA h g−1),
while the stable (1 × 1) tunnel structured β-MnO2 is generally regarded
unfavourable for Zn2+ intercalation due to its narrow tunnels [39].
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Nano Energy 62 (2019) 550–587
However, Chen and co-workers demonstrated that tunneled β-MnO2
undergoes a phase transition to layered zinc-buserite (i.e., B-
ZnxMnO2·nH2O) during the first discharging process, enabling a sub-
sequent intercalation/extraction of Zn2+ ions. By using a Zn(CF3SO3)2
electrolyte with Mn(CF3SO3)2 additive, this tunnel structured β-MnO2
shows a high specific capacity of 225 mA h g−1 and superior cycling
stability with 94% capacity retention over 2000 cycles.
It was found that no matter what the original architecture is, MnO2
hosts usually suffer from serious phase transformation, structural col-
lapse and large volumetric change during the repeated charge and
discharge processes and its original structure will collapse due to the
repeated insertion of a great deal of hydrated Zn2+ ions, resulting in a
rapid capacity fading when cycling. Chen and co-workers proposed a
design of polyaniline (PANI)-intercalated α-MnO2 nanolayers, in which
the guest polymer effectively eliminates the structural collapse and
enhances the stability of layered structure [90]. The as-fabricated PANI-
intercalated MnO2 nanolayers offer a high capacity of 280 mA h g−1
and long-term of over 5000 cycles, representing an effective strategy for
designing stable cathode materials for RZBs.
The second problem of manganese oxides is the continuous dis-
solution of Mn2+ from MnO2 cathode into electrolyte. By the in-
ductively coupled plasma (ICP) technique, Liu and co-workers found
that the concentration of dissolved Mn2+ ions in the electrolyte sig-
nificantly increases in the initial 10 cycles, due to the dissolution of
Mn2+ from electrode materials into the electrolyte upon cycling [24].
Hence, they adopted a “pre-addition” strategy by adding 0.1 M MnSO4
into the pristine ZnSO4 electrolyte to change the dissolution equili-
brium of Mn2+. It is found that the cycling stability of the Zn/MnO2
battery could be greatly enhanced after the pre-addition of Mn2+ ions,
reaching a 5000 cycles lifespan with a high capacity retention of 93% at
5C. This excellent cycling performance can be attributed to the fact that
the pre-added Mn2+ suppress the dissolution of Mn2+ and thus stabilize
the MnO2 electrode. Another effect of pre-added Mn2+ in electrolyte is
that they can be deposited on the electrode surface to increase the mass
of the active material, which contributes to extra capacity and en-
hanced cycling performance. As revealed by Wang and co-workers,
nearly 18.9% of the capacity of the active material is ascribed to the
 H. Li, et al.

Table 2
The comparison for electrochemical performances of representative cathode materials in RZBs.
Electrode Electrolyte Specific capacity Capacity retention/cycles/current density Potential window(V) Reference

α-MnO2 nanofibers 2 M ZnSO4+0.1 M MnSO4 285 mA h g−1 at C/3 92%/5000/5C 1.0–1.9 [24]
α-MnO2 1 M ZnSO4 210 mA h g−1at 0.5C 100%/100/6C 1.0–1.9 [8]
α-MnO2 2 M ZnSO4+0.1 M MnSO4 306 mA h g−1 at 61.6 mAg−1 97%/1000/2772 mA g−1 0.85–1.9 [38]
β-MnO2 3 M Zn(CF3SO3)2 + 0.1 M Mn(CF3SO3)2 258 mA h g−1 at 0.65C 94%/2000/6.5C 0.8–1.9 [39]
β-MnO2 1 M ZnSO4+0.1 M MnSO4 270 mA h g−1 at 100 mAg−1 75%/200/200 mA g−1 1.0–1.8 [40]
γ-MnO2 1 M ZnSO4 285 mA h g-1 at 0.05 mA cm−2 63%/40/0.05 mA cm−2 0.8–1.8 [21]
δ-MnO2 1 M ZnSO4 252 mA h g−1at 83 mAg−1 63%/100/83 mAg−1 1.0–1.8 [41]
Akhtenskite-type MnO2 2 M ZnSO4+0.2 M MnSO4 290 mA h g−1 at 90 mA g−1 99.3%/10 000/6.5C 1.0–1.8 [23]
Todorokite-type MnO2 1 M ZnSO4 108 mA h g−1 at 0.5C 83%/50/50 mAg−1 0.7–2.0 [42]
α-Mn2O3 2 M ZnSO4+0.1 M MnSO4 148 mA h g−1 at 100 mAg−1 68%/2000/2000 mA g−1 1.0–1.9 [43]
Mn3O4 2 M ZnSO4 239.2 mA h g−1 at 100 mAg−1 73%/300/500 mA g−1 0.8–1.9 [44]
ZnMn2O4 3 M Zn(CF3SO3)2 150 mA h g−1 at 50 mA g−1 94%/500/500 mA g−1 0.8–1.9 [45]
Na0.44MnO2 0.5 M ZnSO4+0.5 M NaSO4 186.2 mA h g−1 at 0.2C / 0.5–2.0 [46]
Zn0.25V2O5·nH2O 1 M ZnSO4 282 mA h g−1 at 300 mA g−1 80%/1000/2400 mA g−1 0.5–1.4 [10]
V2O5·H2O/Graphene 3 M Zn(CF3SO3)2 + 0.1 M Vanadium sol 381 mA h g−1 at 60 mA g−1 71%/900 cycles/6000 mA g−1 0.2–1.6 [47]
V2O5 21 M LiTFSI + 238 mA h g−1 at 50 mA g−1 80%/2000/2000 mA g−1 0.2–1.6 [48]
1 M Zn(CF3SO3)2
V2O5 3 M Zn(CF3SO3)2 470 mA h g−1 at 0.2 A g−1 91.1%/4000/5 A g−1 0.2–1.6 [49]
VO2 3 M Zn(CF3SO3)2 357 mA h g−1 at 0.25C 100%/50/0.25C 0.3–1.5 [50]
VS2 1 M ZnSO4 190.3 mA h g−1 at 0.05 A g−1 98%/200/0.5 A g−1 0.4–1.0 [51]

559
V3O7·H2O 1 M ZnSO4 or 0.25 M Zn(CF3SO3)2 in acetonitrile 400 mA h g−1 at 375 mA g−1 80%/200/3 A g−1 (8C) 0.4–1.1 [52]
H2V3O8 @Graphene 3 M Zn(CF3SO3)2 394 mA h g−1 at 1/3C 87%/2000/20C 0.2–1.6 [53]
H2V3O8 3 M Zn(CF3SO3)2 423.8 mA h g−1 at 100 mA g−1 94.3%/1000/5 A g−1 0.2–1.6 [54]
LiV3O8 1 M ZnSO4 256 mA h g−1 at 16 mA g−1 75%/65/133 mA g−1 0.6–1.2 [55]
Zn3V2O7(OH)2·2H2O 1 M ZnSO4 213 mA h g−1 at 50 mA g−1 68%/300/200 mA g−1 0.6–1.8 [56]
Zn2V2O7 1 M ZnSO4 248 mA h g−1 at 50 mA g−1 85%/1000/4 A g−1 0.4–1.4 [57]
Na2V6O16·1.63H2O 3 M Zn(CF3SO3)2 352 mA h g−1 at 50 mA g−1 90%/6000/5 A g−1 0.2–1.6 [58]
Na2V6O16·3H2O 3 M Zn(CF3SO3)2 361 mA h g−1 at 100 mA g−1 80%/1000/14.44 mA g−1(40C) 0.4–1.4 [59]
Na0.33V2O5 3 M Zn(CF3SO3)2 93%/1000/1000 mA g−1 0.2–1.6 [59]

367.1 mA h g−1 at 100 mA g−1

Na1.1V3O7.9@rGO 1 M Zn(CF3SO3)2 238 mA h g−1 at 50 mA g−1 92.9%/100/300 mA g−1 0.4–1.4 [60]
Ca0.25V2O5 1 M ZnSO4 340 mA h g−1 at 0.2C 96%/3000/80C 0.6–1.6 [61]
K2V6O16·2.7H2O 1 M ZnSO4 329.6 mA h g−1 at 200 mA g−1 82%/500/6 A g−1 0.4–1.4 [62]
Na3V2(PO4)3 0.5 M Zn(CH3COO)2 97 mA h g−1 at 0.5C 74%/100/50 mA g−1 0.8–1.7 [63]
Na3V2(PO4)3/C 0.5 M CH3COONa+ 0.5 M Zn(CH3COO)2 97 mA h g−1 at 50 mA g−1 77%/200/50 mA g−1 0.8–1.7 [64]
Na3V2(PO4)2F3 2 M Zn(CF3SO3)2 75 mA h g−1 at 80 mA g−1 95%/4000/1000 mA g−1 0.8–1.9 [65]
LiMn2O4 0.5 M CH3COOLi + 0.5 M Zn(CH3COO)2 129 mA h g−1 at 0.2C 80%/380/2C 1.5–2.1 [66]
LiMn2O4 3 M LiCl +4 M ZnCl2 + 0.1 M KOH 0.32 mA h at 4C 90%/1000/4C 1.5–2.2 [27]
LiMn2O4 Pluronic F77 + 0.25 M Li2SO4 + 0.25 M ZnSO4+ 106 mA h g−1 at 0.5C 83%/300/0.5C 1.4–2.0 [67]
LiMn0.8Fe0.2PO4 21 M LiTFSI + 0.5 M ZnSO4 140 mA h/g at 0.1C 99.3%/150/0.3C 1.0–2.35 [68]
(continued on next page)
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 H. Li, et al.

Table 2 (continued)

Electrode Electrolyte Specific capacity Capacity retention/cycles/current density Potential window(V) Reference

−1
LiFePO4 3 M LiCl +4 M ZnCl2 141 mA h g at 0.6C 65%/450/6C 1–1.4 [69]
LiFePO4/graphene 3 M LiCl +4 M ZnCl2 145.8 mA h g−1 at 0.2C 80%/450/5C 0.5–1.75 [70]
−1
LiFePO4 Pluronic F77 + 0.25 M Li2SO4 + 0.25 M ZnSO4 169 mA h g at 0.1C 90%/300/0.5C 0.9–1.7 [67]
0.25 M CH3COOLi + 0.125 M Zn(CH3COO)2 115 mA h g−1 at 0.5C 99%/40/0.5C 1.0–1.9 [71]

LiNi1/3Co1/3Mn1/3O2
P-Chloranil confinement in CMK-3 1 M Zn(CF3SO3)2 170 mA h g−1 at 43.4 mA g−1 70.3%/200/217 mA g−1 0.8–1.4 [30]
NiHCF 1 M Na2SO4 73.5 mA h g−1 at 100 mA g−1 80%/1000/300 mA g−1 0.9–1.6 [72]
ZnHCF 1 M ZnSO4 65.4 mA h g−1 at 60 mA g−1 81%/100/300 mA g−1 0.8–1.9 [73]
ZnHCF@MnO2 0.5 M ZnSO4 118 mA h g−1 at 100 mA g−1 77%/1000/500 mA g−1 1.4–1.9 [74]
CuHCF 0.02 M ZnSO4 53 mA h g−1 at 60 mA g−1 96.3%/100/60 mA g−1 1.3–2.1 [75]
FeHCF 1 M Zn(CH3COO)2 +in choline acetate with 30 wt% of water 54 mA h g−1 at 0.1 mA cm−2 99%/50/0.1 mA cm−2 0.5–1.8 [76]
NiHCF 0.5 M Zn(ClO4)2 in acetonitrile 55.6 mA h g−1 at 11.2 mA g−1 / 0.7–1.8 [77]
NiHCF 0.5 M Na2SO4 + 0.05 M ZnSO4 76.2 mA h g−1 at 100 mA g−1 81%/1000/500 mA g−1 0.9–1.9 [9]

560
NiCo2O4 1 M KOH+0.02 M Zn(CH3COO)2 183.1 mA h g−1 at 1.6 A g−1 82.7%/3500/5C 1.4–1.9 [78]
Ni @ Ni3S2 1 M KOH+0.02 M Zn(CH3COO)2 150 mA h g−1 at 0.2 A g−1 83.3%/100/0.2 A g−1 1.4–1.9 [34]
Ni @ NiO 1 M KOH+0.02 M Zn(CH3COO)2 0.422 mA h cm−2 at 8 mA cm−2 92.5%/1800/8 mA cm−2 1.4–2.0 [79]
PPy 0.5 M KCl + 0.1 M Zn(CH3COO)2 123 mA h g−1 at 1900 mA g−1 38%/200/4400 mA g−1 0–1.2 [80]
PPy 0.1 M NH4Cl + 0.1 M sodium citrate 0.085 mA h cm−2 at 0.1 mA cm−2 / −0.5–0.8 [81]
PANi/graphite 1.0 M ZnCl2 and 0.5 M NH4Cl 142.4 mA h g−1 at 0.6 mA cm−2 70%/200/0.6 mA cm−2 0.7–1.7 [82]
Ni foam supported PANi 1 M ZnSO4 + 0.3 M (NH4)2SO4 183.28 mA h g−1 at 2.5 mA cm−2 91%/50/5 mA cm−2 0.7–1.6 [83]
Calix [4]quinone 3 M Zn(CF3SO3)2 335 mA h g−1 at 20 mA g−1 87%/1000/500 mA g−1 0.8–1.3 [84]
Poly(benzoquinonyl sulfide) 3 M Zn(CF3SO3)2 203 mA h g−1 at 20 mA g−1 86%/50/40 mA g−1 0.2–1.8 [85]
P-Chloranil confinement in CMK-3 1 M Zn(CF3SO3)2 170 mA h g−1 at 43.4 mA g−1 70.3%/200/217 mA g−1 0.8–1.4 [30]
MoS2@ 1 M ZnSO4 202.6 mA h g−1 at 0.1 A g−1 98.6%/600/1000 mA g−1 0.3–1.5 [86]
Carbon cloth
Nano Energy 62 (2019) 550–587
H. Li, et al.
Fig. 11. SEM and TEM images of manganese-based oxides. (a) α-MnO2. Reproduced with permission [24]. Copyright 2016, Springer Nature; (b) β-MnO2. Reproduced
with permission [40]. Copyright 2017, Royal Society of Chemistry; (c) δ-MnO2. Reproduced with permission [41]. Copyright 2015, Elsevier; (d) Mn2O3. Reproduced
with permission [43]. Copyright 2017, Elsevier; (e) Mn3O4. Reproduced with permission [25]. Copyright 2018, Royal Society of Chemistry; (f) ZnMn2O4. Reproduced
with permission [45].Copyright 2016, American Chemical Society.
contribution of pre-added Mn2+, and this kind of “extra contribution”
should not be neglected [91].
Another strategy to alleviate dissolution of Mn2+ is surface coating
and modification. Mai and co-workers developed graphene scroll-
coated α-MnO2 as cathode material for RZBs [92]. The graphene scroll
was uniformly coated on the MnO2 nanowires with an average thick-
ness of 5 nm, which effectively mitigate the dissolution of the dissolu-
tion of Mn2+ from Mn3+ disproportionation during cycling. This can be
evidenced by an inductively coupled plasma (ICP) analysis of the Mn
and Zn element concentration in ZnSO4 electrolyte. The concentration
of the dissolved Mn element of MnO2 decreased after coating with
graphene scroll, suggesting that graphene scroll-coated MnO2 is more
stable than pristine MnO2 as the cathode for aqueous ZIB. As a result,
the long-term cycling stability of Zn–MnO2 battery was greatly en-
hanced, achieving a high capacity retention of 94% after 3000 cycles at
3 A g−1. The third strategy to mitigate the Mn dissolution is in-
corporation of metal ions and defects. Recently, Liang and co-workers
reported a potassium ion (K+)-stabilized and oxygen-defect manganese
oxide as a durable cathode material for RZBs [93]. The ICP analysis
result of the Mn concentration in a 2 M ZnSO4 electrolyte confirmed
that the introduction of K+ ions could significantly suppress the Mn
dissolution during cycling. In addition, the oxygen defects could greatly
enhance electrochemical reactivity and reaction kinetics of manganese
oxide, leading to an impressive durability over 1000 cycles with no
obvious capacity fading.
Another issue is the controversial energy storage mechanism of
MnO2 cathode which has been a subject of debate. As mentioned be-
fore, various mechanisms have been proposed for MnO2 cathodes: Zn2+
intercalation/deintercalation mechanism (α/γ-MnO2); co-insertion of
Zn2+ and H+ mechanism (akhtenskite-MnO2, polyaniline-intercalated
MnO2); conversion reaction mechanism (α-MnO2). More comprehen-
sive investigation is needed to reach a consensus on the energy storage
mechanism of MnO2 for RZBs.
Recently, manganese sesquioxide (Mn2O3) with Mn3+ state was
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Nano Energy 62 (2019) 550–587
reported by Kang and co-workers. It showed a reversible capacity of
148 mA h g−1 at 100 mAg−1, which is much lower than MnO2 cathode
materials [43]. The energy storage mechanism investigation revealed
that the pristine α-Mn2O3 with Mn(III) undergoes a reversible phase
transformation from a bixbyite structure to a layered-type zinc birnes-
site with Mn(II) during the Zn2+ intercalation processes. Cation-de-
fective spinel ZnMn2O4 was also investigated as a Zn-insertion cathode
material in aqueous Zn(CF3SO3)2 electrolyte. GITT test suggested that
the introduction of Mn vacancies was peculiarly beneficial for Zn2+
diffusion in the spinel framework and contributed to faster reaction
kinetics. As a result, the cation-defected ZnMn2O4 spinel achieved a
reversible specific capacity of 150 mA h g−1 at 0.05 A g and a high ca-
pacity retention of 94% up to 500 cycles [45]. These results show that
the exploration of cation-defective spinel compounds may be a pro-
mising direction for RZBs and cation defects play a critical role in en-
hancing the electrochemical performance of electrode materials for
multivalent ions energy storage.
To briefly summarize, manganese oxides generally suffer from two
major issues when used as cathode materials for aqueous RZBs: 1).
Serious phase transformation, structural collapse and large volumetric
change during the repeated charge and discharge processes; 2). Mn
dissolution. To tackle these problems, many strategies have been de-
veloped, including polymer-reinforced layered structure, pre-addition
of Mn2+ ions, surface coating or modification, and incorporation of
metal ions and defects. Furthermore, the reaction mechanism of MnO2
cathode is controversial and under debate, and more electrochemical
approaches and advanced characterization techniques as well as precise
theoretical calculations are needed to disclose the charge-storage me-
chanism of manganese oxides for RZBs.
3.2. V-based cathode materials
V-based compounds exhibits various oxidation states including V5+,
V , V3+ and V2+ and these valences can be interconverted. Due to the
4+
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 12. (a) SEM image of Zn0.25V2O5·nH2O; (b) Cycling performance of Zn0.25V2O5·nH2O cathode at 2.4 A g−1, the inset is its crystal structure. (c) Rate performance
of Zn0.25V2O5·nH2O cathode. Reproduced with permission [10]. Copyright 2016, Springer Nature. (d) SEM image of V2O5·nH2O. (e) The crystal structures of pristine
V2O5·nH2O and V2O5·nH2O at charged and discharged states. Reproduced with permission [47]. Copyright 2016, Wiley-VCH. (f) SEM image of Ca0.25V2O5·nH2O, the
inset is its crystal structure; (g) The electrical conductivity of Ca0.25V2O5·nH2O and Zn0.25V2O5·nH2O; (h) Cycle performance of Ca0.25V2O5·nH2O at a rate of 80C; (i)
SEM image of Na2V6O16·3H2O. Reproduced with permission [61]. Copyright 2018, Wiley-VCH.

distortion of V–O coordination polyhedral and the conversion of diverse
oxidation states, V-based compounds exhibit broader variation range
and higher specific capacity when they are used as electrode materials
for energy storage applications [94]. The past two years have witnessed
tremendous progress in the development of V-based compounds as
cathode materials for aqueous RZBs, which includes VO2 [50], V2O5
[47–49], V3O7·H2O [52], V6O13 [95], V10O24·12H2O [96], VS2 [51,97],
H2V3O8 [53], LiV3O8 [55], Zn0.25V2O5·nH2O [10], Zn2V2O7 [57],
Zn3V2O7(OH)2·2H2O [56], Ca0.25V2O5·nH2O [61], and Na2V6O16·3H2O
[58]. Traditionally, V-based materials possess low stability (especially
in aqueous electrolyte), poor conductivity and low ions diffusion
coefficient, which gives rise to a poor long-term cycling performance.
However, the Zn0.25V2O5·nH2O cathode (Fig. 12 a and b) reported by
Nazar's group offers a high capacity of 282 mA h g−1 at 0.3 A g−1 and
good rate capability as well as a superior long-term cyclability (81%
capacity retention over 1000 cycles) [10]. This remarkable electro-
chemical performance can be ascribed to the following factors: (1) The
structural water molecules intercalated in the interlayers of vanadium
oxide bronze plays a vital role in buffering the high charge density of
divalent Zn2+ ions, lowering electrostatic interactions, and expanding
the interlayer spacing of layered vanadium oxide, contributing to fast
Zn2+ diffusion and high rate performance; (2) The interlayer Zn2+ ions
in the layered oxide and structural water can act as “pillars” to stabilize
vanadium oxide framework, thereby preventing structural collapse
during cycling and enhancing the cycling stability of V-based materials;
(3) The unique 1D nanobelt morphology with high aspect ratio facil-
itates the charge transfer at the electrode/electrolyte interface and
shortens the Zn2+ diffusion pathways, thus favoring the excellent rate
performance.
Lately, the critical role of structural water in enhancing the per-
formance of V-based materials is also demonstrated by Yang and co-
workers [47]. Benefiting from charge shield and “lubricating” effect of
the structural water, the as-prepared V2O5·nH2O delivers significantly
improved rate and cycling performance (71% capacity retention over
900 cycles). To capitalize the “pillar” effect of the intercalated metal
ions, Alshareef and co-workers designed a double-layered
Ca0.25V2O5·nH2O as a novel cathode material for RZBs [61]. The in-
tercalated Ca2+ further enlarge the cavity size between V2O5 inter-
layers and significantly improve the electrical conductivity of vanadium
oxide (as high as 185 S m−1), which boost the Zn2+ (de)intercalation
during the cycling process. The as-prepared Ca0.25V2O5·nH2O cathode
exhibits excellent long-term cycling performance with an expressive
capacity retention of more than 96% over 3000 cycles even at a high
rate of 80C, suggesting good structural stability. After that, “pillar”-
induced stability was also demonstrated in other V-based materials such
as NaV3O8·1.5H2O [98], Na1.1V3O7.9 [60], Na2V6O16·3H2O [59],
Na2V6O16·1.63H2O [58], K2V6O16·2.7H2O [62], MgxV2O5·nH2O [99],
and Ag0.4V2O5 [100].
Besides, various V-based compounds without structural water and
“pillar” effects, such as V2O3 [101] and ZnxMo2.5+yVO9+z [102] have
been explored as cathode materials for aqueous RZBs. From the afore-
mentioned studies, it can be concluded that most of V-based compounds
demonstrate attractive electrochemical performance in terms of high
specific capacity (around 200–400 mA h g−1, higher than Mn-based

562
H. Li, et al.
Fig. 13. Schematic illustration of Zn2+ intercalation/deintercalation into PBAs. Reproduced with permission [3]. Copyright 2018, Wiley-VCH.
materials), good rate capability (better than Mn-based cathodes), and
long cycling life. Despite these promising properties, they usually suffer
from lower operation voltages (around 0.6–1.0 V, lower than Mn-based
materials), and the toxicity of vanadium-based materials is also an
issue, which limit their wide application in aqueous RZBs. Another
problem is that many V-based materials suffer from strong electrostatic
interactions between the host lattice and Zn2+ ions, leading to sluggish
Zn2+ diffusion kinetics. More feasible strategies for vanadium-based
materials that lower their electrostatic interactions with multivalent
ions should be developed.
3.3. Prussian blue analogs-based cathode materials
Prussian blue analogues (PBAs), as a series of compounds derive
from Prussian blue (PB) after substitutional and interstitial modifica-
tion, which can be roughly denoted as AxMAy[MB (CN)6]z·nH2O (A is
alkali metal; MA and MB are transition metals such as Mn, Fe Co, Ni, Cu,
and Zn, as illustrated in Fig. 13) [103]. Due to their three-dimensional
(3D) porous framework structures, sufficient reaction sites, diverse
valence states and unique structural stability as well as easy prepara-
tion, PBAs have received growing attention in energy storage devices
[104].
In 2014, Liu and co-workers investigated zinc hexacyanoferrates
(ZnHCFs) with the rhombohedral structure as cathode materials for
RZBs, in which the ZnN4 tetrahedra are connected to the FeC6 octa-
hedra via CN ligands (C≡N) to form a porous three-dimensional fra-
mework [73]. This structure enables the reversible insertion/extraction
of Zn2+ ions. The ICP and XRD tests further revealed that 0.85 mol
Zn2+ was intercalated into 1 mol Zn3[Fe(CN)6]2 during the discharging
process. Then, a reversible deintercalation process of Zn2+ was ob-
served when charging. The Zn/ZnHCFs battery offers a high average
operation voltage of around 1.7 V and 65.4 mA h g−1 at 60 mA g−1 as
well as good rate capability (Fig. 14).
Mantia and co-workers proposed a zinc-ion battery based on a
copper hexacyanoferrate (CuHCF) cathode in a low concentration of
ZnSO4 electrolyte, showing a specific energy density of 45.7 Wh kg−1 at
60 mA g−1 and a high capacity retention of 96.3% over 100 cycles at 1C
with an average discharge potential of 1.73 V [75]. The electrochemical
reaction can be expressed as follows:
KCuFe(CN)6 + x Zn2+ + 2x e− ↔ ZnxKCu[Fe(CN)6]1–2x[Fe(CN)6]2
(17)
x Zn ↔ x Zn2+ + 2x e− (0 ≤ x ≤ 0.5)
2+
When Zn is intercalated into the crystal structure of CuHCF, two
low-spin Fe3+ are reduced simultaneously into low-spin Fe2+. Similar
Nano Energy 62 (2019) 550–587
mechanism was revealed by Wang et al. for CuHCF nanocubes [105].
By means of cyclic voltammetry (CV) and XPS measurements, they
demonstrated that the Zn2+ insertion/extraction into/from CuHCF is
dominated by the solid phase diffusion process, accompanied by the
Fe3+/Fe2+ redox reaction. Opposite to the preliminary studies that
capacity fading is related to the active material dissolution, Mantia
et al. observed the analysis of the differential specific charge profiles
and ascribe the capacity fading to the phase transition of CuHCF [106].
Recently, by operando synchrotron XRD, Renman and co-workers
confirmed that structural changes of CuHCF are associated with the
possibility of Zn2+ swapping positions between the tunnels and the
vacant Fe(CN)6 sites in the CuHCF framework [107].
Apart from ZnHCF and CuHCF, Hong et al. also demonstrated that
Zn2+ can be reversible inserted into nickel hexacyanoferrate (NiHCF) in
an organic-electrolyte-based system, with lower voltage plateau
(∼1.2 V) and lower specific capacity (∼56 mA h g−1) compared with
ZnHCF and CuHCF [77]. To improve the performance of NiHCF cath-
odes, Ma et al. developed a hybrid rechargeable Na–Zn hybrid battery
using NiHCF as cathode, in which Na+ ions rather than Zn2+ ions were
intercalated/deintercalated into/from the NiHCF cathode and a Zn
deposition-dissolution process take places in the zinc anode at the same
time. Benefitting from this hybrid chemistry, this battery delivered a
specific capacity of 76.2 mA h g−1 and a good cycling stability with
81% capacity retention over 1000 cycles [9].
Despite some attractive advantages such as high voltage, low cost,
and ease of fabrication, PBAs based materials are still afflicted with
relatively lower specific capacity (typically less than 80 mA h g−1) and
lower energy density than other energy storage systems. Besides, PBAs
run the risk of decomposing to form highly toxic cyanide CN− under
strongly acidic condition, which may hinder their large-scale applica-
tion.
3.4. Lithium/sodium intercalated cathode materials
As mentioned before, lithium or sodium intercalated compounds
can act as cathodes in aqueous hybrid Zn batteries via coupling with
dual ion based-electrolytes and a metallic Zn anode. In 2012, Chen and
co-workers proposed a LiMn2O4//Zn battery hybrid battery, which
composes of a LiMn2O4 as cathode, a metallic Zn anode and an aqueous
binary electrolyte containing Li+ and Zn2+ (Fig. 15 a-b) [27]. The as-
prepared hybrid Zn battery realizes a high operation voltage of 2 V and
good long-term cycling stability (95% capacity retention over 4000
cycles). Lately, they fabricated a binder-free flexible electrode con-
(18)
sisting of high-aspect-ratio carbon nanotubes and LiMn2O4 nano-
particles as cathode materials for rechargeable hybrid aqueous battery
[108]. Benefiting from this robust network architecture and good
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H. Li, et al.
Fig. 14. (a) Schematic diagram of the ZnHCF–Zn battery; (b) CV curves of Zn and ZnHCF (2 mV s−1); (c) GCD profiles at 60 mA g−1 for Zn anode (blue), ZnHCF (red)
and the full cell (black) in 1 M ZnSO4; (d) Rate performance; (e) Cycle life tests at 60 mA g−1 (square) and 300 mA g−1 (circle). Reproduced with permission [73].
Copyright 2014, Wiley-VCH.
electrical conductivity, the hybrid Zn battery delivers a discharge ca-
pacity of 72 mA h g−1 at 20C and an excellent rate performance.
Inspired by this hybrid design, Bakenov and co-workers engineered
an aqueous battery with an olivine LiFePO4, a Zn anode and an opti-
mized Li+/Zn2+ binary electrolyte (Fig. 15 c-d). The as-prepared Zn/
LiFePO4 battery demonstrates a prolonged cycle span (over 400 cycles)
as well as a superior rate capability (up to 60C) [69]. The reaction
equation can be expressed as follows:
LiFePO4 ↔ Li+ + FePO4 + e−
Zn 2+ -
+ 2e ↔ Zn
After that, Cui's group developed a high-voltage Zn/LiMn0.8Fe0.2PO4
battery based on a highly concentrated “water-in-salt” electrolyte, in
which two reversible reactions of Li+ extraction/insertion can be
achieved in this aqueous system [68]. This battery possesses a high
operating voltage exceeding 1.8 V which is higher than Zn/LiFePO4
Nano Energy 62 (2019) 550–587
battery and delivers a specific energy density of 183 Wh kg−1.
Apart from that, polyanion compounds, such as NASICON-struc-
tured M3V2(PO4)3 (M = Li, Na), have gained increasing interest as
promising cathode alternatives for aqueous RZBs due to their stable
structure, plenty of vacancies, and relatively higher redox voltage.
Huang's group proposed a novel hybrid aqueous battery constructed
with a Na3V2(PO4)3 cathode, a Zn anode and a 0.5 M Zn(CH3COO)2
electrolyte, in which zinc ion intercalation mechanism is mainly con-
trolled by a diffusion process [63]. The Na3V2(PO4)3/Zn battery rea-
(19)
lized a specific capacity of 97 mA h g−1 with a 1.1 V operating voltage
(20) but suffered from a relatively low cycling stability (74% capacity re-
tention ratio after 100 cycles at 0.5C). More recently, Jiang and co-
workers reported a high-performance fluorine-doped Na3V2(PO4)2F3
cathode, which offered improved electrochemical performances in
terms of high voltage (1.62 V), good energy density (97.5 W h kg−1),
and long-term stability (95% capacity retention over 4000 cycles) [65].
Other lithium and sodium-based materials such as LiNi1/3Co1/3Mn1/
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H. Li, et al.
Fig. 15. (a) CV profiles of LiMn2O4/Zn battery; (b) charge-discharge curves of the full LiMn2O4//Zn battery tested at 1.1 mA cm−2; Reproduced with permission
[27]. Copyright 2012, Elsevier. (c) Schematic diagram of the Zn/LiFePO4 hybrid battery (d) Rate performance of the Zn/LiFePO4 hybrid battery. Reproduced with
permission [69]. Copyright 2015, Elsevier.
3 O2were introduced in aqueous hybrid Zn batteries [71]. Overall, the
LiMn2O4//Zn battery can offer much higher voltage than other lithium
or sodium based materials, while fluorine-doped Na3V2(PO4)2F3 has
better long-term stability. This hybrid design is helpful to broaden the
scope of high-performance cathode material research for RZBs.
3.5. Nickel-based and cobalt-based cathode materials
Due to diverse oxidation states, high electrochemical activity and
highly reversible redox reactions, nickel (Ni)-based (Ni oxides, hydro-
xides, sulfide) and cobalt (Co)-based compounds have been regarded as
promising materials for aqueous energy storage systems. Integration of
Ni-based and Co-based compounds into energy storage devices, espe-
cially rechargeable alkaline batteries, provides opportunities to meet
the ever-growing demands for green power sources with superior rate
capability, long cycle life, high safety, and high energy density. Among
them, rechargeable Ni–Zn and Co–Zn batteries are particularly ad-
vantageous due to their relatively higher operation voltage (around
1.8 V) and higher energy density compared with other aqueous re-
chargeable batteries. So far, many Ni-based and Co-based materials
including NiO [109], Ni3S2 [34], Ni(OH)2 [110], NiCo2O4 [78],
Co3O4@NiO [111], NiAlCo-layered double hydroxide [112] and Co3O4
[32] have been employed as cathode materials targeting on achieving
high-performance Ni–Zn batteries.
For example, Lu and co-workers developed a highly reversible and
flexible Ni–NiO//Zn yarn battery with a hetero-structured Ni–NiO
cathode, offering excellent cycling stability both in aqueous and
polymer electrolytes (Fig. 16a–f) [109]. Furthermore, a high energy
density of 6.6 μWh cm−2 is obtained by the flexible quasi-solid-state
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Nano Energy 62 (2019) 550–587
Ni–NiO//Zn fiber battery, opening new opportunities for flexible and
wearable energy storage devices. Wu and co-workers demonstrated a
long-life Zn//Co3O4 battery using ultrathin porous Co3O4 nanosheets
on Ni foam as cathode and an electrodeposited zinc on carbon fibers as
anode (Fig. 16h), which exhibited a high energy density of
241 W h kg−1 and good cycling performance (80% capacity retention
after 2000 cycles) [32]. During the charging process, soluble zincate
ions [Zn(OH)4]2− are reduced into Zn and Co3O4 is simultaneously
reverted to CoO2 by two-step reactions with OH−. Upon discharging,
Zn reacts with OH− anions to form zincate ions [Zn(OH)4]2−, and the
CoO2 was reduced to Co3O4 at the meantime. These electrochemical
reactions in these two electrodes can be described by the following
equations:
Negative electrode:
2[Zn(OH)4]2- + 4e- ↔ 2Zn + 8OH- (21)
Positive electrode:
Co3O4 + OH- + H2O ↔ 3CoOOH + e− (22)
-
3CoOOH +3OH ↔ 3CoO2 + 3H2O + 3e -
(23)
Total reaction:
Co3O4 + 2[Zn(OH)4]2- ↔ 2Zn + 3CoO2 + 2H2O + 4OH- (24)
Nanostructured electrode materials (e.g. nanoparticles, nanowires,
nanorods and nanobelts) offer unique chemical, mechanical and elec-
trical properties including high surface area and shorter pathways for
ions and electrons transportation, and hold the key for addressing the
intrinsic issues of bulk materials, such as poor electrical conductivity
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 16. (a) SEM image of the Ni–NiO cathode; (b and c) TEM images of the Ni–NiO cathode; (d and e) schematic representation and SEM image of the Ni–NiO//Zn
yarn battery, respectively; (f) cycling test of the Ni–NiO//Zn yarn battery. Reproduced with permission [109]. Copyright 2017, Wiley-VCH. (g) CV curves of Zn anode
and Co3O4 electrodes. (h) Cycling performance of Zn//Co3O4 battery at 1 A g−1. Reproduced with permission [32]. Copyright 2016, Wiley-VCH.

and large volume expansion of electrodes [113]. Besides, rationally
structural and componential design of electrode materials will sig-
nificantly increase the electrochemical performance and cyclic stability
of batteries. For Ni–Zn batteries, both α-Ni(OH)2 and β-Ni(OH)2 show
hexagonal structures. α-Ni(OH)2 compose of Ni(OH)2-x layers with po-
sitive charge and intercalated anions to obtain neutrality is a hydro-
talcite-like compounds, whereas β-Ni(OH)2 exhibits a well-ordered
brucite-like structure without any intercalated molecules. The cyclic
stability of zinc-ion batteries using β-Ni(OH)2 cathode is much better
than that of α-Ni(OH)2 cathode [33]. Interestingly, nanosized β-Ni
(OH)2 brings about the higher capacity than micro-sized β-Ni(OH)2
[114]. In addition, surface modification also can enhance zinc-ion
batteries’ performance. For example, Lu and co-workers synthesized
ultrathin nickel cobaltite (NiCo2O4) nanosheets with enriched oxygen
vacancies and surface phosphate ions (P–NiCo2O4-x) by annealing
NiCo2O4 nanosheets under phosphating atmosphere and used it as
cathode for zinc-ion batteries [35]. Oxygen vacancies not only act as
shallow donors to improve the electrical conductivity of NiCo2O4, but
also provide more active sites. More importantly, the introduced
phosphate ion decreases the electron transport energy, thus sig-
nificantly enhancing the surface reactivity and kinetics. As a result, the
optimized P–NiCo2O4-x cathode delivers remarkable capacity of
309.2 mA h⋅g−1 at 6.0 A g−1 and excellent rate performance at large
current density.
However, further developments of Ni–Zn or Co–Zn batteries are
greatly plagued by their relatively lower specific capacity and

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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 17. (a) Discharge/charge curves of the as-prepared Zn–C4Q battery at the current density of 0.02 A g−1. (b) CV curves of Zn–C4Q battery at various scan rate. (c)
Cycling performance of Zn–C4Q battery with a Nafion separator at 0.5 A g−1. Reproduced with permission [29]. Copyright 2018, American Association for the
Advancement of Science. (d) Schematic diagram of the structure and reaction mechanism of the aqueous PTO//Zn battery. (e) Ex-situ FTIR spectra of PTO cathode at
discharged and charged states. Reproduced with permission [115]. Copyright 2018, Wiley-VCH.

Coulombic efficiency due to the severe deterioration of the Ni-based specific capacity (336 mA h g−1), high energy density (186.7 Wh kg−1)
materials and zinc dendrite formation during repeated cycles, which as well as long-term cycling stability (over 1000 cycles). Besides, poly
should be tackled in the future. (benzoquinonyl sulfide) (PBQS) has also been investigated as a cathode
material for RZBs, showing a high specific capacity of 203 mA h g−1 at
0.1C [85]. Density functional theory (DFT) calculations suggests that a
3.6. Organic cathode materials
reversible bonding of Zn2+ ions with O atoms in C]O groups is taking
during the redox reactions of PBQS cathode.
Very recently, organic materials have been investigated as low-toxic
Apart from these materials, conductive polymers such as polyaniline
and sustainable cathode alternatives to conventional inorganic cathode
(PANI) [83,116], polypyrrole (PPy) [81,117] and other materials in-
materials for RZBs applications. Chen and co-workers reported an
cluding Co(III) rich-Co3O4 [118], MoS2 [86,119], CoS6 [120], and Ti-
aqueous zinc battery using a Calix [4]quinone (C4Q)-cathode
substituted tungsten molybdenum oxide (MTWO) [121] have also been
(Fig. 17a–c), which provides a high specific capacity of 335 mA h g−1 at
explored as cathode materials for RZBs.
20 mA g−1 and a long-life span up to 1000 cycles with a capacity re-
According to the previous discussion, we can draw the following
tention of 87% [84]. They utilized the ESP method to calculate the
conclusions:
active sites of C4Q when used as cathode material for RZBs. It is known
that electrophilic reactions prefer to take place in the active sites with
(1) In terms of specific capacity, V-based materials generally have
more negative ESP. In other words, the sites with more negative ESP are
larger specific capacities among different cathode materials
more favorable for discharge reaction as it involves Zn2+ uptake [29].
(around 200–400 mA h g−1), while Mn-based materials possesses
For organic C4Q material, the carbonyl groups are the active sites due
relatively lower specific capacities (around 150–300 mA h g−1).
to the fact that they have lower ESP than that of bilateral carbonyls,
Prussian blue analogues and Li+/Na+ intercalated cathode mate-
suggesting that they may have strong interactions with Zn2+ ions
rials usually have the lowest specific capacities.
(Fig. 16c–g).
(2) As for operation voltage, Li+/Na+ intercalated cathode materials
In situ ATR-FTIR spectroscopy, Raman spectroscopy, and UV–vis
and some Prussian blue analogues (e.g. CuHCF, ZnHCF) have high
spectroscopy were employed to investigate the structural evolution,
operation voltage in neutral or mildly acidic electrolyte, while V-
dissolution behavior, and charge-storage mechanism of C4Q cathode. It
based materials suffer from lower working potentials (about
is revealed that carbonyl groups at the bottom and up of C4Q will ac-
0.2–1.6 V). It is worth noting that Ni, Co, or Ag-based materials that
cept electrons accompanied by storing Zn2+ ions during the discharge
operated in alkaline electrolyte usually have high voltage, mainly
process. Upon charging, C4Q will be oxidized and hence the captured
due to the fact that zinc has more negative potential in alkaline
electrons and Zn2+ ions will be released. However, due to the inherent
environments.
soluble characteristic of discharged products of C4Q in aqueous elec-
(3) For reaction mechanisms, V-based materials and Prussian blue
trolyte, an expensive cation-exchange membrane (Nafion) must be
analogues are mainly based on reversible Zn2+ insertion/extrac-
employed as a separator to inhibit the cross of C4Q2x− and prevent the
tion. For hybrid batteries that coupling a lithium or sodium based-
zinc anode from poisoning by discharge products, which limits its large-
intercalation cathode with a metallic Zn anode, they operate based
scale applications.
on a hybrid chemistry and two different electrochemical processes
More recently, Xia et al. developed an environment-friendly and
have been involved: Zn deposition-dissolution in anode and Li+ or
flexible Zn battery based on a pyrene-4,5,9,10-tetraone (PTO) cathode,
Na+ -induced oxidization/reduction in cathode. While the reaction
in which conventional porous glass fiber membrane can be used as
mechanism of Mn-based materials remains controversial and has
separator (Fig. 17d and e) [115]. The Zn/PTO battery showed a high

567
H. Li, et al.
Fig. 18. (a) Schematic diagram of the AC based Zn-ion capacitor [122]. Copyright 2018, Elsevier. (b) TEM image of the prepared bio-derived AC (the inset in b is the
corresponding selected area electron diffraction (SAED) of the AC) [123]. Copyright 2017, Elsevier. (c) Schematic of the fabrication process for the Zn-ion micro-
supercapacitor. The SEM images of the (d) pristine CNT paper, (e) microelectrode and (f) Zn anode after plating [124]. Copyright 2018, The Royal Society of
Chemistry.
been a subject of debate. Since then various mechanisms for MnO2
cathode have been reported: Zn2+ intercalation/deintercalation
mechanism; co-insertion of Zn2+ and H+ mechanism; conversion
reaction mechanism. More detailed work and more advanced
characterization techniques are required to reach a consensus on
the energy storage mechanism of MnO2.
3.7. Capacitor-type materials for Zn-ion capacitors
Recently, a novel energy storage system of zinc-ion hybrid super-
capacitors has been proposed, in which capacitor-type materials such as
activated carbon (AC) and metallic Zn are employed as cathode and
anode, respectively. The operation mechanism is based on the si-
multaneous adsorption/de-adsorption at the capacitor-type cathode
and deposition/dissolution of Zn in the anode. Based on this design, Xu
and co-workers constructed a aqueous Zn-ion capacitor, which em-
ployed commercial AC, metallic zinc, and ZnSO4 as cathode, anode and
electrolyte, respectively (Fig. 18a) [122]. This zinc-ion hybrid super-
capacitor integrated advantages of supercapacitors and batteries:
Firstly, it provides better rate capability and cycling stability than most
of rechargeable batteries (over 10000 cycles). Secondly, it offers much
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Nano Energy 62 (2019) 550–587
larger capacity and higher energy density than conventional super-
capacitors. Similarly, Tang et al. develop an organic Zn-ion capacitor
based on a highly porous bio-derived AC. Fig. 18b shows the TEM
image of the as-prepared AC that has a homogeneous porous structure.
By optimizing the weight ratio of activating agent, the specific surface
area of bio-derived AC can be as high as 3554 m2 g−1, which con-
tributed to a high specific capacitance [123]. Recently, Qu and co-
workers designed a zinc-ion micro-supercapacitor with a capacitor-type
carbon nanotube (CNT) micro-cathode (Fig. 18c–f). The oxygen func-
tional groups on the surface of the CNT micro-cathode can not only
enhance the wettability but also offer a large additional pseudo-capa-
citance, since these functional groups can electrochemically interact
with divalent Zn2+ ions [124].
Anode: Zn ↔ Zn2+ + 2e− (25)
Cathode: CNT···O + Zn 2+
+ 2e −
↔ CNT···O···Zn (26)
2+
At the CNT micro-cathode, divalent Zn ions are adsorbed/des-
orbed with those oxygen functional groups of CNT during the cycling
process. While at the Zn anode part, a reversible Zn deposition-dis-
solution process takes place at the same time. As a result, the prepared
H. Li, et al.
Fig. 19. Schematic illustration of (a) the structure of zinc-air battery. Gas diffusion layer integrated with electrocatalysts: (b) carbon-based (cross-sectional view), and
(c) metal-based (top view). Reproduced with permission [37]. Copyright 2017, Wiley-VCH. Hair-like array of Co3O4-carbon nanotube/stainless steel air electrode: (d)
Schematic diagram and (e) SEM images. Reproduced with permission [131]. Copyright 2016, Wiley-VCH.
zinc-ion micro-supercapacitor achieved a high energy density of
29.6 W h cm−2 and a high power density of 8 mW cm−2. The design of
high-rate, high capacity, and long-life Zn-ion capacitors is believed to
open up a new avenue for next-generation energy storage devices.
3.8. Bifunctional air electrode for rechargeable zinc-air battery
Zinc-air batteries exhibit significantly high-energy density, owing to
that the reactants (oxygen) of air electrode are from outside of battery
[125–128]. For that, air electrode provides reaction places for oxygen
evolution reaction (OER) and oxygen reduction reaction (ORR), which
was regarded as the most important component and inevitably de-
termines the performance of a Zn–air battery [129,130]. The OER takes
place at two-phase boundaries (liquid electrolyte-solid catalyst). The
ORR occurs at three-phase boundaries (air-liquid electrolyte-solid
electrocatalyst) of air electrode, which is in intimate contact with gas
phase and liquid phase (Fig. 19a). The hydrophobic side provides mi-
crochannel to facilitate air diffusion to catalytic sites and barriers to
prevent electrolyte leakage. The hydrophilic side offers access to ion-
conductivity electrolyte. Although the conventional electrodes can be
employed for OER, it cannot supply sufficient three-phase boundaries to
sustain continuous and high-current-density ORR, leading to rather
ineffective as air electrodes. In addition, OER and ORR of air electrode
mainly determine the electrochemical performance of rechargeable
zinc-air battery. During discharging process, the air electrode consumes
oxygen molecular of air (ORR process). Reversely, the air electrode
evolves oxygen (OER process) during charging process. Usually, the
ORR and OER is slow during discharge-charge process. The integration
of electrocatalysts to air electrode is required to accelerate ORR and
OER reaction. Thus, a typical air electrode is composed of a gas diffu-
sion layer and a catalyst layer. The gas diffusion layer normally pro-
vides both pathway for air diffusion, and physical and conductive
support for electrocatalysts. Meanwhile, the electrocatalysts accelerate
the ORR and OER. In the following sections, the design of the gas-dif-
fusion layers and the exploitation of bifunctional catalysts are dis-
cussed.
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Nano Energy 62 (2019) 550–587
3.8.1. Gas-diffusion layer for zinc-air batteries
In zinc-air batteries, the gas-diffusion layer plays important roles
including supporter for electrocatalysts, transportation of air/oxygen,
barriers to prevent the leakage of liquid electrolyte and current col-
lector as an electrically conductive pathway. Therefore, an interfacial
structure with optimal hydrophilicity and hydrophobicity in each side
is critical to gas-diffusion layer. The basic requirement of gas-diffusion
layer contains high porosity for gas diffusion, excellent electrical con-
ductivity for charge collection, high mechanical strength and reliable
electrochemical oxidation stability and chemical durability in strong
alkaline electrolytes.
Normally, gas-diffusion layer is composed of several polytetra-
fluoroethylene (PTFE)-bonded carbon layers on one side of current
collecting materials (usually metal or carbon-based materials) to realize
hydrophobicity. The widely used gas-diffusion layer in zinc-air batteries
are woven carbon fiber cloth (CFC) (Fig. 19b) and metal-based mate-
rials (Fig. 19c). The CFCs typically have a dual layer design, composed
of a macroporous gas-diffusion backbone and a thin microporous layer.
The macroporous backbone consists of a highly hydrophobic array of
graphitized carbon fibers or carbon particles to provide large gas-dif-
fusion channels. Whereas, the thin microporous layer is made up by
relatively hydrophilic carbon layer with fine porosity to support the
electrocatalysts. The thicker CFC gas-diffusion layer not only tends to
have better battery performance but also exhibits enhanced mechanical
flexibility. Thereby, it can be utilized as a supporter of robust electro-
catalysts for small-scale, flexible zinc-air battery applications. However,
poor stability in strong alkaline electrolyte is a major problem for
woven CFC-based gas-diffusion layer. CFC gas-diffusion layers are
highly susceptible to carbon corrosion, leading to losses of active sur-
face area for electrochemical oxygen reactions, irregular distribution of
current throughout the air electrodes, and even the leakage of liquid
electrolyte. Furthermore, alkaline electrolytes also can be negatively
affected by dissolved carbonate species, owing to carbon corrosion of
gas-diffusion layers.
For long-term stability, it is needed to prevent the corrosion of the
gas-diffusion layer by the utilization of metallic substrates as the al-
ternatives, including nickel/copper foam, nickel mesh, stainless-steel
H. Li, et al.
(SS) mesh, and titanium mesh. The metallic substrate-based gas-diffu-
sion layer could provide high electrical conductivities and electro-
chemical oxidation resistance over a wider potential range compared to
CFC-based gas-diffusion layers, which could offer comparable battery
performance to CFC-based gas-diffusion. For example, Chen's group
developed an air electrode with hair-like catalysts vertically and di-
rectly grown on a flexible stainless steel mesh (Fig. 19d and e) [131].
The SS mesh and the direct growth of carbon nanotube significantly
improve electrical conductivity and mechanical flexibility of gas dif-
fusion layer, which extend the limits of nanostructured catalysts based
on conventional planar air electrodes.
3.8.2. Bifunctional electrocatalysts for zinc-air battery
For rechargeable zinc-air battery, the ORR takes place at triple
phase boundary among air electrode, oxygen gas and liquid electrolyte.
The generated OH− will migrate to metallic Zn anode and reacts with
Zn. These reactions are reversed with zincate ions back to metallic Zn
and the evolution of oxygen [132]. The reactions are summarized as
follows:
Cathode: O2 + 2H2O +4e- 4OH-, E = 0.4V vs. SHE.
Anode: Zn + 2OH- ZnO + H2O + 2e-; E = −1.26V vs. SHE.
Total reaction: 2ZnO 2Zn + O2, E = 1.66V
Parasitic reaction: Zn + 2H2O Zn(OH)2 + H2.
According to the reaction mechanism, the theoretically operational
voltage is ∼1.66 V. However, its practical operating voltage always is
lower than 1.2 V to sustain a rational discharge current. The recharge
voltage is about 2 V or higher to reverse above mentioned reaction. The
large voltage gap between charge and discharge is mainly caused by the
large overpotential of oxygen reaction at the air cathode [133]. Such
large overpotential mainly originates from the activation loss in air
cathode, which can be minimized by developing high-efficiency ORR
and OER electrocatalysts. So, air electrodes should be able to catalyze
both the ORR and OER kinetics efficiently, which can be realized uti-
lizing mixture of two components or a bifunctional oxygen electro-
catalysts. Moreover, the major issues that occur in Zn anode which
include dendrite growth, shape change, passivation, and hydrogen
evolution are also key factors for the high voltage gap of Zn-air battery.
These issues and corresponding remedy strategies will be discussed in
detail in Section 4.
Commercial Pt/C electrocatalyts exhibit excellent ORR perfor-
mance, but the OER performance is poor, which owes to the formation
of oxide layer, resulting in low electrical conductivity. The state-of-art
IrO2 and RuO2 electrocatalysts possess high OER activity; however,
their ORR activity is significantly low. The mixture of Pt/C/IrO2 or Pt/
C/RuO2 can be used to fabricate rechargeable zinc air batteries.
However, it is not possible for practical applications due to the ex-
pensive noble metal electrocatalysts. In addition, the durability of the
electrocatalysts remains a major challenge.
An elctrocatalyst with dual functions (ORR and OER) from a single
component, named bifunctional electrocatalyst, have become the main
targets for practical application of the zinc air batteries. In recent years,
the bifunctional electrocatalysts have been widely studied including
metal-free materials (nitrogen, phosphorus, sulfur and boron-doped
carbon materials), transition metal-based material (metal oxide, metal
nitride, metal sulfide and metal selenides) and some composite mate-
rials. Among them, heteroatoms doped carbon materials and the M-N-C
(M = Co, Fe) are representatives with high electrocatalytic activities for
zinc air batteries. For example, Zhi's group reported a hierarchically
micro-, meso- and macroporous nitrogen, sulfur doped carbon material
via a one-pot pyrolysis reaction (Fig. 20a–d) [134]. The hierarchically
porous carbon materials were simply synthesized by in-situ pyrolysis of
a mixture precursor of silica spheres, Teflon powder and trithiocyanuric
acid (TA). It shows both excellent ORR and OER performance (with a
metric potential difference of 0.72 V in 1 M KOH aqueous solution
medium). When the bifunctional electrocatalysts were utilized for a Zn
air battery, the battery could execute the discharge/charge process with
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small voltage gap and shows excellent cycling stability. Dai's group
developed a metal-free bifunctional electrocatalyst, nitrogen and
phosphorus co-doped mesoporous carbon foams by template-free ap-
proach (Fig. 20e–h) [135]. They found a scalable approach to fabricate
3D heteroatoms doped carbon foams by simple pyrolysis of the poly-
aniline with the existence of phytic acid. The resultant electrocatalyst
possesses large surface area (∼1663 m2 g−1) and shows good electro-
catalytic properties for both ORR and OER. When it is used in air
electrode of a zinc air battery, the batteries showed open circuit of
1.48 V and could be cycled stably for 180 cycles at 2 mA cm−2.
Zhang's group reported a flexibly freestanding cobalt-based air
electrode of in-situ coupling of strung Co4N and intertwined N–C fibers
by pyrolysis of the novel pearl-like ZIF-67/polypyrrole nanofibers net-
work immobilized on CFC (Fig. 20i-m) [136]. The air electrode can be
directly used for flexible zinc air batteries, which show excellent elec-
trochemical performance and mechanical flexibility, due to the high
ORR and OER performance of air electrode and flexibility of air elec-
trode. For flexible/wearable application, the volume expansion and
contraction of electronic devices may occur. So, a compressible battery
is required to accommodate stress. Zhi's group developed a compres-
sible zinc air battery based on single-site iron based bifunctional oxygen
catalysts (Fig. 20n-p) [137]. The single-site electrocatalysts could pro-
vide abundant active sites and highly electrocatalytic activities of each
active sites, resulting in high ORR/OER performance. The compressible
zinc air battery is constructed based on the developed oxygen catalysts
and polyacrylamide (PAM) hydrogel, which shows excellent charge/
discharge process with 0.78 V voltage gap.
4. Zn anode
The advantages of Zn as anode for batteries include its large
abundance, low cost, environmental friendliness, low oxidation-reduc-
tion potential as well as good reversibility in aqueous electrolyte. As an
essential component, Zn anode greatly affects the performance of RZBs.
In this part, we will introduce the fundamental electrochemistry as well
as the issues and challenges facing Zn electrode, followed by the stra-
tegies and corresponding effects for improving the Zn anode perfor-
mance.
4.1. Electrochemical fundamentals and issue of zinc anode
To understand the fundamental electrochemistry and performance-
limiting phenomena occurring on the Zn electrode, it is necessary to
study the Pourbaix diagram of Zn in aqueous environment (Fig. 21a),
which presents the possible stable (equilibrium) phases in different pH
range and equilibrium conditions [17]. The diagram shows that Zn is
thermodynamically unstable in aqueous solutions and it is liable to
dissolve accompanied by the H2 evolution among the whole pH range.
Under acidic conditions (pH < 4.0, zinc has high solubility and can
easily dissolve into Zn2+ ions. At 5.0 < pH < 8.0, the dissolution of
Zn becomes relatively slower due to the high overpotential and the
lower corrosion activity compared with strong acid solution. Under
neutral or slightly alkaline solutions (8.0 < pH < 10.5), the dissolu-
tion of Zn decreases and more stable Zn corrosion products are gener-
ated (e.g., Zn(OH)2). The main reaction of Zn anode in acid and neutral
solutions can be written as:
Zn ↔ Zn2+ + 2e- (27)
In alkaline environment (pH > 11), zinc solubility increases again
and the formation of zincate ions (e.g., Zn(OH)42−) is favored and
oxygen reduction reaction dominates the cathodic corrosion process.
Different from the electrochemical behaviors in neutral or mildly acidic
solutions, the zinc electrodes undergo a solid-solute-solid transforma-
tion in alkaline electrolytes (ZnO–Zn(OH)42--Zn), which inherently
faces a series of challenges: (i) the discharge product ZnO passivates the
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 20. Nitrogen, sulfur codoped porous carbon electrocatalysts: (a) Schematic illustration of synthetic procedure, (b) OER and ORR performance, (c) charge/
discharge profile of zinc air battery and (d) cycling stability of zinc air battery. Reproduced with permission [134]. Copyright 2017, The Royal Society of Chemistry.
Nitrogen, phosphorus doped carbon materials: (e) schematic illustration of synthetic procedure, (f) OER and ORR performance, (g) schematic illustration of the
structure of zinc air battery and (h) long-time durability of Zn air battery. Reproduced with permission [135]. Copyright 2015, Springer Nature. Strung Co4N and
intertwined N–C fibers electrocatalysts: (i–k) SEM images, (l) photograph of the cable-type Zinc-air battery at various bended and twisted conditions, and (m) charge/
discharge profile of zinc-air battery at different bending angles. Reproduced with permission [136]. Copyright 2015, American Chemical Society. Single-site active
iron-based bifunctional oxygen catalyst: (n) Schematic illustration of synthetic procedure, (o) ORR and OER performance and (p) charge/discharge cycling profile at
different compress strains. Reproduced with permission [137]. Copyright 2018, American Chemical Society.

surface of Zn, which lowers the utilization of zinc active materials; (ii) Zn + 4OH- ↔ Zn(OH)42- + 2e- (28)
non-uniform dissolution and deposition of zinc occurs in random lo-
Zn(OH)42- ↔ ZnO + H2O + 2OH -
(29)
cations of electrode surface, leading to severe electrode morphology
change and dendrite growth after continuous cycling [138]. The anodic Accompanied by the dissolution process of Zn electrode, four major
reaction in alkaline media is expressed by the following equations: performance-limiting phenomena occur during the battery operation
(Fig. 21b), which includes: 1) dendrite growth, 2) shape change, 3)

Fig. 21. (A) Pourbaix diagram of Zn–H2O system at 25 °C. Reproduced with permission [17]. Copyright 2018, American Chemical Society. (B) Schematic illustration
of four major issues that may occur on the zinc electrode: (a) dendrite growth, (b) shape change, (c) passivation, and (d) hydrogen evolution. Reproduced with
permission [37]. Copyright 2017, Wiley-VCH.

571
H. Li, et al.
passivation and increased internal resistance, and 4) hydrogen evolu-
tion [37]. It should be noted that hydrogen evolution is much severe in
alkaline zinc batteries than in neutral ones. The Zn/ZnO standard re-
duction process in alkaline electrolytes and the hydrogen-evolution
reaction (HER) can be described by the following equations:
Zn + 2OH- → ZnO + H2O + 2e- (−1.26 V vs. SHE) (30)
2H2O + 2e- → 2OH- + H2 (−0.83 V vs. SHE) (31)
It can be seen that the standard reduction potential of Zn/ZnO
(−1.26 V) is much lower than that of HER (−0.83 V). Therefore, the
HER process is thermodynamically favored and hydrogen evolution will
inevitably take place during the operation of RZBs, which can result in
consumption of the zinc and electrolyte during cycling. This undesired
side reaction also results in a low Coulombic efficiency of zinc elec-
trode, since the HER will consume some electrons that transferred to
the zinc anode and generate hydrogen. Suppression of hydrogen evo-
lution is essential for zinc-based batteries, especially for alkaline RZBs
and Zn-air batteries. It is found that the actual rate of hydrogen evo-
lution is determined by its exchange current density and overpotential
[139]. Therefore, strategies to increase the overpotential and decrease
exchange current density for hydrogen evolution should be developed
to improve the charging efficiency and reduce the self-discharge rate of
the zinc electrode. Apart from hydrogen evolution, other issues such as
dendritic growth, shape change, and passivation could also result in
severe capacity fading and poor Coulombic efficiency of RZBs, which
drives the implement of various remedy strategies to enhance the Zn
anode performance.
4.2. Additives for Zn anode & Zn alloy anode
One facile and efficient way to improve the property of Zn anode
that is to incorporate certain additives with the Zn anode. These ad-
ditives generally have an important effect on the crystal growth, mor-
phology and structure of Zn deposition. Metallic Hg is an effective
additive for suppressing self-corrosion and hydrogen evolution of Zn
anode, but it has been prohibited in many products including batteries
due to its high toxicity and environmental concerns. As an alternative
solution, alloying zinc with other metals (e.g., Bi, Sn, In, or Ni) was
found to be an effective way to suppress H2 generation and alter the
electrochemical properties of Zn anode [140]. Besides, some metal
compounds (such as BaO, Bi2O3, In(OH)3, Ca(OH)2, Zn4Al
(OH)10]2(CO3)·nH2O) have also been considered as the promising ad-
ditives to stabilize the Zn anode [141]. These additives usually have
higher hydrogen overpotential than Zn, which could improve the
electrochemical performance of Zn anode and suppress H2 generation
to different degrees. For example, by in situ XRD technique, Brousse
et al. demonstrated that Bi2O3 could be reduced to metallic bismuth and
form a nanometer scale conductive network prior to the Zn deposition,
thus optimizing the current distribution and promoting the uniform
deposition of zinc (Fig. 22a–c) [142].
Carbon-based materials (such as carbon black, activated carbon) are
sometimes introduced to Zn anode to avoid passivation and improve the
electrochemical performance of Zn anode. Li et al. demonstrated that
introducing activated carbon (AC) into the Zn anode can significantly
improve the reversibility and suppress the formation of zinc hydroxide
sulfate hydrates (Zn4SO4(OH)6·nH2O) (Fig. 22d–f) [143]. In addition, it
is found that the rich and well-developed pores of the AC could ac-
commodate the deposition of Zn dendrites and insoluble anodic pro-
ducts, contributing to an enhancement of the cycling stability of the
rechargeable Zn/MnO2 battery.
4.3. Surface modification
Surface modification of Zn particles or Zn plate provides another
effective strategy for improving the comprehensive properties of the Zn
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Nano Energy 62 (2019) 550–587
anode. This approach could improve the utilization ratio of additives
and enhance the surface and bulk properties, rendering electrode ma-
terials more stable. Recently, various nanocomposites, including or-
ganic materials, metals and metallic compounds, have been studied as a
protective layer to modify Zn-based electrodes, achieving long life and
high efficiency RZBs [144].
Kang et al. designed a porous nano-CaCO3 coating as a protective
layer to achieve a uniform and bottom-up Zn stripping/plating (Fig. 23)
[145]. This strategy effectively suppresses the development of zinc
dendrites that may cause large polarization and internal short circuit,
thus improving the Coulombic efficiency and cycling stability of Zn
batteries. The as-fabricated rechargeable Zn–MnO2 battery with a
CaCO3-coated Zn anode offers a 177 mA h g−1 at 1 A g−1 after 1000
cycles, which is much higher than the one with bare Zn anode
(124 mA h g−1).
Mai and co-workers proposed an atomic layer deposition (ALD)
coating strategy to design an ultrathin protective TiO2 coating for zinc
metal anode [146]. The highly conductive and amorphous TiO2 layer
could act as a stable buffer layer between the Zn anode and electrolyte
and effectively suppress the hydrogen evolution and the formation of
inactive reaction by-products, leading to an enhanced electrochemical
performance of Zn based batteries. By virtue of this protective TiO2
layer, the as-prepared Zn–MnO2 battery exhibited a greatly enhanced
cycling performance (85% capacity retained after 1000 cycles at
3 mA cm−2).
4.4. Structural design of Zn anode
The geometry and structure design of the zinc anode play an im-
portant role in mitigating the issue of shape change and zinc dendrite
formation and lowering the internal electrical resistance. In principle,
increasing the surface area of the Zn anode can decrease the zinc-de-
position overpotential, thus minimizing the potential for zinc dendrite
formation and passivation. Besides, the porous structure and large
surface area is beneficial for enhancing the interfacial contact between
Zn and the electrolyte and shortens the ion diffusion pathways, there-
fore improving the utilization ratio of Zn based materials. To date,
various types of high-surface-area Zn electrodes have been investigated,
including fine powders, spheres, flakes, ribbons, fibers, and foams
[147].
Zhang and co-workers developed a spin cast approach to fabricate
various forms of Zn electrodes, such as Zn fibers, rods, bars and sheets
with different thickness and lengths [148]. These fibrous and porous Zn
anodes are especially advantageous for large-sized alkaline based Zn
batteries due to their high mechanical stability and flexibility and high
effective surface area. Long and Rolison and their co-workers prepared
a highly porous, 3D zinc sponge electrode to enhance the zinc utiliza-
tion and rechargeability (Fig. 24) [149]. This 3D porous architecture
increased the electrified active area and minimized the local current
density, thus suppressing the formation of zinc dendrites. In addition,
the zinc deposition can be well controlled and restricted within the void
space of 3D Zn sponge architecture, which diminished the potential for
shape change upon cycling. Benefiting from this unique 3D architecture
design, this Zn sponge electrode maintained a dendrite-free mor-
phology after high-rate cycling up to 188 mA h g−1 (based on Zn
electrode) and exhibited a high Zn utilization (about 90%) in a primary
Zn-air battery. Based on this advanced 3D Zn sponge electrode, Rolison
and co-workers further designed a high-energy-density, economically
feasible nickel–3D Zn rechargeable battery [150]. At deeper depth of
discharge (≥40% DODZn), this advanced Ni–3D Zn battery can deliver
a high a specific energy which is competitive with common Li-ion
batteries. For “start-stop” operation applications, this Ni–3D Zn battery
could achieve more than 50,000 cycles, demonstrating excellent relia-
bility and great application potential.
Recently, Fan and co-workers electrodeposited Zn nanoflakes array
(≈20 nm in thickness and ≈400 nm in width) on a 3D porous graphene
H. Li, et al.
Fig. 22. (a) SEM image of Zn/Bi2O3 mixed electrode before test. (b) SEM image of Zn/Bi2O3 mixed electrode after 10 cycles. (c) Comparison of cycling performance
for Bi2O3-free Zn electrode (empty squares) and Zn/Bi2O3 mixed electrode (plain squares). Reproduced with permission [142]. Copyright 2013, Elsevier. (d)
Schematic illustration for the deposition of anodic products in activated carbon. (e) SEM image of bare anode after cycling, showing lots of zinc dendrites. (f) SEM
image of AC-modified Zn anode after cycling. Reproduced with permission [143]. Copyright 2015, The Electrochemical Society.
foam. This structure has two advantages over traditional Zn foil: First,
3D porous graphene foam serves as both a light-weight backbone for
zinc array deposition and a continuous current flow channel as well as
macroporous agent to diminished the formation of Zn dendrites and
inactive surface by-products, leading to an enhanced Coulombic effi-
ciency and cycling stability. Second, the high surface area, and more
reactive sites features of this 3D zinc structure contribute to the fast Zn/
Zn2+ redox kinetics, thus enhancing high rate performance of Zn anode
[151].
However, as the exposed surface area increase, the hydrogen evo-
lution rate and the corrosion rate of the zinc electrode will increase
accordingly. This side reaction will consume zinc active materials and
electrolyte, aggravate self-discharge and eventually shorten battery life-
span. Recently, Liu and co-workers developed several deeply re-
chargeable Zn anodes with unique core/shell structures for alkaline Zn
batteries which solving the dilemma of Zn passivation and dissolution
simultaneously [152]. For example, a sealed ZnO@TiNxOy nanorod
anode was prepared by a hydrothermal and atomic layer deposition
(ALD) technique. This structure possesses a few merits: (i) The small
size (< 500 nm) of ZnO prevents passivation and allows full utilization
of active materials; (ii) the carbon paper framework and TiNxOy
coating, which encapsulates ZnO nanorod, function as an electrical
pathway so that all ZnO nanorods are electrochemically active; (iii) the
thin TiNxOy coating enables fast hydroxide/water diffusion and coating
mitigates Zn dissolution in alkaline electrolyte, thus preventing anode
structure fracture. Besides, ion-sieving carbon nanoshell coated ZnO
nanoparticle anode [153], pomegranate-structured ZnO@C [154], and
lasagna-structured ZnO anode [155] were also reported, aiming at
solving the dilemma of Zn passivation and dissolution simultaneously
and achieving deeply rechargeable Zn based batteries.
5. Electrolytes for rechargeable Zn based batteries
Generally, RZBs operate in neutral or mildly acidic electrolyte (such
as ZnSO4 or Zn(NO3)2) and alkaline electrolytes (such as KOH or
NaOH). To enhance the reversibility of Zn batteries and suppress cor-
rosion and dendritic growth, many additives are adopted. With the
increasing demands for long-term cycling stability of RZBs as well as
flexible and wearable electronics, hydrogel or gel electrolytes and ionic
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liquid (IL) based electrolytes have been proposed and evaluated. In this
part, we will discuss composition and additives of conventional aqu-
eous electrolytes as well as their influence on battery performance. The
selection of hydrogels and ionic liquids, rational design for multi-
functions, as well as the performance in RZBs will also be discussed.
5.1. Neutral or mildly acidic electrolytes
Since the electrolyte governs the battery electrochemistry, the
search of proper electrolyte system plays a pivotal importance in de-
veloping high performance RZBs. The use of aqueous electrolyte offers
many advantages, such as high security, low cost, ease of battery as-
sembly, and most importantly, high ionic conductivities, which is cru-
cial for the high rate performance of RZBs. Traditionally, RZBs have
been developed employing KOH or NaOH aqueous alkaline electrolyte,
such as rechargeable alkaline Zn–MnO2 or Ni–Zn batteries [156].
However, the principal problems with aqueous alkaline electrolyte are
the high dissolution and corrosion of the zinc electrode. Strong acidic
electrolytes are also ruled out considering the high corrosion reactivity
of Zn. Therefore, the implement of aqueous neutral or mildly acidic
electrolyte has the following advantages: (1) reduces zinc dendrite
formation, leading to high Coulombic efficiency; (2) decreases the
corrosion to Zn anode, which is beneficial for long-term cycling stabi-
lity; (3) possesses high safety, low cost and high ionic conductivity
compared with organic electrolytes.
Zinc salt and its concentration in the electrolyte solution exert
profound effect on the electrochemical performance of aqueous zinc
batteries. To date, zinc salts including ZnSO4, Zn(NO3)2, Zn(CH3COO)2,
ZnF2, Zn(ClO4)2, ZnCl2 and Zn(CF3SO3)2 have been explored [157], as
listed in Table 1. It is reported that nitrate ions are strong oxidants,
which will oxidize the Zn foil anode and degrade the performance of
copper hexacyanoferrate cathode while Zn(ClO4)2 has higher over-
potential of zinc dissolution/deposition [106]. Zinc acetate is a com-
monly used additive for food supplements, thus exhibits good en-
vironmental compatibility. However, its featureless performance can't
support its wide application [157]. As for ZnF2 and ZnCl2, their appli-
cation is limited by low solubility in water and instability of Cl-, re-
spectively. The most commonly used zinc salt is ZnSO4 due to its low
cost, high solubility in water and their remarkable battery performance.
H. Li, et al.
Fig. 23. SEM images of (a–c) bare and (d–f) nano-CaCO3-coated Zn electrode (a,d) before and (b,c and e,f) after 100 cycles. The white arrow in (c) points a Zn
dendrite detaching from the Zn foil. (g) Schematic diagram of morphology evolution for bare and CaCO3-coated Zn electrodes upon repeated stripping/plating
cycling. Reproduced with permission [145]. Copyright 2018, Wiley-VCH.
However, its usage in Zn batteries is always accompanied by the for-
mation of basic zinc sulfates, Zn4(OH)6SO4·nH2O, which is considered
to be responsible for the capacity loss in the initial several cycles [57].
Recently, Zn(CF3SO3)2 emerged as a favorable electrolyte for RZBs.
Chen and co-workers compared the CV profiles of Zn electrode in 1 M
Zn(CF3SO3)2 electrolyte and 1 M ZnSO4 electrolyte (Fig. 25a–d) [45].
Compared to ZnSO4, Zn(CF3SO3)2 electrolyte shows smaller peak se-
paration between Zn deposition/dissolution and higher peak current
density, indicating enhanced reaction kinetic for Zn deposition/dis-
solution and better reversibility. This is mainly due to the fact that
bulky CF3SO3−anions can reduce the number of water molecules sur-
rounding Zn2+ cations and decrease the solvation effect, thus facil-
itating the Zn2+ transportation and charge transfer. Moreover, in-
creasing salt concentration could reduce the water activity and water-
induced side reaction, thus leading to improved cycle stability. How-
ever, it is worth mentioning that high concentration electrolyte lead to
high viscosity, which will decrease the ionic conductivity of the elec-
trolyte and is unfavourable for the rate performance of batteries.
Moreover, Zn(CF3SO3)2 is much more expensive than ZnSO4 and other
conventional zinc salts, which may hinder its large scale application.
Recently, Xu reported a highly concentrated Zn ion electrolyte
consisting of 1 mol L−1 Zn(TFSI)2 and 20 mol L−1 LiTFSI (Fig. 25e and
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Nano Energy 62 (2019) 550–587
f) [158]. This neutral electrolyte not only promotes dendrite-free Zn
plating/stripping at nearly 100% Coulombic efficiency, but also capable
of retaining water in an open atmosphere. When paired with LiMn2O4
or O2 cathodes, the former demonstrates a high energy density of
180 Wh kg−1 and capacity retention of 80% for > 4000 cycles, whereas
the latter achieves an energy density of 300 Wh kg−1 for > 200 cycles.
The structural and spectroscopic studies combined with molecular-scale
modelling revealed that the high population of anions forces them into
the vicinity of Zn2+ to form close ion pairs (Zn–TFSI)+ that sig-
nificantly suppress the presence of (Zn–(H2O)6)2+, thus H2 evolution is
effectively prevented, which leads to excellent Zn reversibility.
The addition of additives into the electrolyte is another approach to
mitigate the Zn dendrite growth and the dissolution of cathode mate-
rials. For example, MnSO4 is usually added into the ZnSO4 electrolyte to
suppress the dissolution of Mn based cathodes in Zn–Mn battery sys-
tems [24]. Hu reported the suppression of zinc dendrites in an aqueous
solution with imidazolium ionic liquids as additive [159]. The added
imidazolium ionic liquids can be adsorbed on the electrode surface or
freshly formed deposit surface, thus altering the chemical double layer
and blocking zinc nucleation. It is revealed that after adding imidazo-
lium ionic liquids, both nucleation overpotential and polarization ex-
tent increase in the order of additive-free < 1-ethyl-3-
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 24. (a) Photograph (left one) and SEM images (middle and right) of a 3D Zn-sponge electrode. (b) Schematic diagram for conventional and 3D Zn electrodes
upon charge and discharge processes. Reproduced with permission [149]. Copyright 2014, The Royal Society of Chemistry. (c) Schematic diagram of morphological
changes of the ZnO@TiNxOy nanorod anode during cycling. The structure of Zn anode retains very much during cycling with the protection of thin TiNxOy coating
[152]. Copyright 2018, Elsevier.

methylimidazoliumchloride (EMI-Cl) < 1-ethyl-3-methylimidazolium
hexafluorophosphate (EMI-PF6) < 1-ethyl-3-methylimidazolium bis
(trifluoromethanesulfonyl)imide (EMI-TFSA) < 1-ethyl-3-methylimi-
dazolium dicyanamide (EMI-DCA). Niu and co-workers revealed that
the addition of Na2SO4 into the ZnSO4 electrolyte can inhibit the dis-
solution of NaV3O8·1.5H2O in the cathode and suppress the dendrite
deposition in the Zn anode [98]. This is because Na+ with a lower
reduction potential than Zn2+ could form a positively charged elec-
trostatic shield around the initial growth tip of the protuberances of Zn,
which forces further deposition of Zn to adjacent regions, thus elim-
inating the Zn dendrite formation.
5.2. Alkaline electrolytes
Alkaline electrolytes are highly attractive for RZBs due to their
various merits such as high operation voltage, fast reaction kinetics,
and higher ionic conductivity in comparison with neutral and acidic
electrolytes. The commonly used alkaline electrolytes in RZBs include
KOH, NaOH, and LiOH.38 Among them, the KOH solution has been the
most widely studied one, due to the high solubility of zinc salts as well
as higher ionic conductivity of K+ (73.50 Ω−1 cm2 equiv−1) than Na+
(50.11 Ω−1 cm2 equiv−1) and Li+ (38.70 Ω−1 cm2 equiv−1)
[139,160,161]. Furthermore, the by-products of KOH electrolyte with
CO2 demonstrates a higher solubility than that of NaOH counterpart,
which could thereby alleviate the carbonate precipitation issues for Zn
batteries. The way to enhance the conductivity of the alkaline elec-
trolyte is to increase the concentration of KOH aqueous solution.
However, the high solution concentration can lead to increased visc-
osity of the electrolyte and the formation of ZnO, which reversibly re-
duces ion conductivity of electrolyte and form zinc dendrites. There-
fore, 6 M KOH aqueous solution is widely employed as electrolyte for
Zn based alkaline batteries.
Despite the aforementioned benefits, zinc solubility, which is asso-
ciated with zinc dendritic formation, shape changes and zinc passiva-
tion, has been a critical obstacle for achieving long-life and high-effi-
ciency alkaline RZBs [162]. Owing to the gravitational force, the
migration of Zn from top and side of Zn electrode to bottom, leading to
the irreversible capacity loss and triggering the formation of Zn

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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 25. (a and b) CV curves of Zn anode in 1 M Zn

(CF3SO3)2 and 1 M ZnSO4 at 0.5 mV s−1, respec-
tively; (c) comparison of the cycling performance of
Zn/Zn symmetrical cells at 0.1 mA cm−2 in 3 M Zn
(CF3SO3)2 and 3 M ZnSO4 electrolytes; (d) compar-
ison of the rate performance in 3 M Zn(CF3SO3)2 and
3 M ZnSO4 electrolytes. Reproduced with permission
[45]. Copyright 2016, American Chemical Society.
(e) SEM image of Zn electrode in 1 mol L−1 Zn
(TFSI)2 and 20 mol L−1 LiTFSI after 500 cycles. (f)
The cycling stability and Coulombic efficiency of the
Zn/LiMn2O4 full cell in 1 mol L−1 Zn(TFSI)2 and
20 mol L−1 LiTFSI at 4C. Reproduced with permis-
sion [158]. Copyright 2018, Springer Nature.

Fig. 26. Morphologies of deposited-Zn in 7 M KOH solution with 0.6 M ZnO addition at different current density for different times: (a) at 100 mA cm−2 for 10 min;
(b) at 50 mA cm−2 for 20 min; (c) at 20 mA cm−2 for 50 min and (d) at 10 mA cm−2 for 100 min. Morphological control of zinc redistribution at 100 mA cm−2 for
10 min: (e) tree/leaf-like dendritic morphology in static electrolyte; (f) morphology of deposited Zn in flow electrolyte; (g) boulder-like morphology in static
electrolyte and morphology of deposited Zn at 60 °C. Reproduced with permission [163]. Copyright 2015, The Royal Society of Chemistry.

dendrites. The uniform Zn electrode surface, especially Zn dendrites
easily penetrate the separator, leading to electrical short circuit. The Zn
electrode shape changes and Zn dendrites are important issues in al-
kaline RZBs. The dendritic morphology often varies with the ion spe-
cies. Their morphology often perpendicularly directs to the separator or
cathode surface with boulder-like, tree-like or leaf-like shapes. This
because that the binding energy of Zn atoms in a certain orientation is
stronger than that of other direction. The growth of Zn dendrites relies
on local overpotential, which is related to electric potential between the
anode and cathode as well as interface interaction between Zn electrode
and electrolyte. The higher voltage is applied, the faster growth rate of
Zn dendrites will be. For example, as Wang and their co-workers re-
ported, dendrite propagation is significantly controlled by ion-diffusion,
which depends on overpotential of electrolyte and surface energy ani-
sotropy. Furthermore, the morphology of dendrites can also contribute
to nonuniform distribution of the electric field and ion concentration of
electrolyte [163]. As shown in Fig. 26, different morphologies of Zn
surface can be achieved at different charge current densities and dif-
ferent states of the electrolyte. From Fig. 26a–d, it is observed that leaf-
like morphology easily forms at high current density. The effect of
electric field force on depositing atoms becomes stronger with the in-
crease of electrochemical reaction rate, resulting in more dendrites on

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H. Li, et al.
Fig. 27. SEM image comparison of Zn anode electrodeposited at electrolytes containing 9 M KOH +5 wt% ZnO (a) without and (b) with 0.5 wt % EMI-DCA.
Reproduced with permission [171]. Copyright 2015, Elsevier.
both sides of main stems. In addition, electrolyte management and
charging mode can affect the growth of dendrites. As show in
Fig. 26e–h, the flowing electrolyte, higher-temperature electrolyte and
pulsating current charge mode can change the direction and rate of
dendrite growth and the morphology of Zn electrode.
Extensive efforts have been devoted to mitigating these issues by
adding some special additives to alkaline electrolytes. For example,
additives including borate (K3BO3), fluoride (KF), phosphate (K3PO4),
and carbonate (K2CO3) have been proven to be effective to reduce the
zinc solubility and enhance the cycling life of alkaline RZBs
[156,164–166]. Another strategy is to fabricate organic-inorganic hy-
brid electrolyte like CH3OH–KOH, surfactants-KOH electrolytes, al-
tering the growth of zinc moss and dendrites [167–170]. In addition,
the introduction of surfactants or ionic liquids (such as 1-ethyl-3-me-
thylimidazolium dicyanamide (EMI-DCA)) into alkaline electrolytes
have been regarded as another effective way for alleviating the solu-
bility of Zn anode by controlling interfacial structure of Zn and elec-
trode passivation (Fig. 27) [171].
5.3. Ionic liquid and organic electrolytes
Room temperature ionic liquids (ILs) are molten salts in liquid state
at near-ambient temperature. They typically consist of bulky, asym-
metric organic cations and organic/inorganic anions and offer many
attractive features like low vapor pressure, nonflammability, high
thermal stability, wide electrochemical stability window, and relatively
high ionic conductivity with respect to other non-aqueous electrolytes.
A significant research has been carried out on using ILs as potential
electrolytes for lithium ion batteries. The reversible deposition/strip-
ping of Zn from ILs have also been demonstrated, thus, ILs have been
considered as promising electrolyte alternatives to conventional aqu-
eous or organic electrolytes for RZBs.
The morphology of Zn deposits is strongly dependent on the cations and
anions. Liu investigated the effect of anion on the morphology of zinc de-
posits [172]. Twisted nanowire-like structures were obtained in 0.2 M Zn
(TFSI)2/1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([EMIm]TFSI). Hexagonal plate-like zinc structures with the plates per-
pendicular to the substrate are obtained in 0.2 M Zn(CF3SO3)2/1-ethyl-3-
methylimidazolium trifluoromethylsulfonate([EMIm]TfO). While cauli-
flower-like compact zinc films were gained in 0.2 M Zn(OMs)2/1-ethyl-3-
methylimidazolium methylsulfonate ([EMIm]OMs). It can be seen that the
morphologies of Zn deposits were quite different and tended to be more
compact by varying anions from TFSI− via TfO− to OMs−. As investigated
by far-infrared spectroscopy, Raman spectroscopy and AFM, the speciation
of Zn2+ ions in ILs largely depends on the solvation power of the anion and
the strength of the interaction between Zn2+ ions and anions. In the in-
vestigated zinc salts and ILs, the strength of the interaction between Zn2+
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Nano Energy 62 (2019) 550–587
ions and anions is in the order TFSI− < TfO− < OMs−, which leads to
different morphologies of Zn deposits.
The cations of ILs have also been shown to have a great effect on the
electrodeposition of zinc and the electrode/electrolyte interfacial
properties. For example, the deposition of Zn in 1-ethyl-3-methylimi-
dazolium trifluoromethylsulfonate ([EMIm]TfO) leads to dense hex-
agonal micro crystalline deposits, while Zn deposits in 1-butyl-1-me-
thylpyrrolidiniumtrifluoromethylsulfonate ([Py1,4]TfO) shows flower-
like nanocrystalline morphology. This may be attributed to the fact that
interaction of [Py1,4]+ cations with the deposition substrate is stronger
than the one of [EMIm]+ cations with the substrate, which can lead to
the difference in the morphology of the obtained deposits. The stronger
adsorption of [Py1,4]+ to the surface of the growing nuclei might lead
to a nanocrystalline deposition [173]. Endres also investigated the de-
position of Zn in Zn(CF3SO3)2/([Py1,4]TfO) solution using gold or ITO
glass as substrate and a deposition temperature of 125 °C [174]. How-
ever, zinc nanowires were obtained this time, which is different from
the above flower-like nanocrystalline morphology.
The electrodeposition of zinc from ILs in the presence of an additive
was proved to be an effective way in improving the deposition process
and the morphology of the deposits. On one hand, the additives can
ligate with the metal species, forming a complex, which is more difficult
to be reduced. On the other hand, they are adsorbed on the electrode
surface, which will change the electrochemical double layer structure
and alter the metal nucleation process. Endres reported the addition of
Ni(CF3SO3)2 to Zn(CF3SO3)2 in [EMIm]TfO to obtain dendrite-free Zn
deposits with a nanocrystalline structure (Fig. 28) [175].
Abbott investigated the effect of additive addition on the Zn elec-
trodeposition process in choline chloride: ethylene glycol and choline
chloride: urea [176]. The ammonia and ethylene diamine were de-
monstrated to be effective brighteners for Zn deposition and produces
micro-crystalline deposits due to their ability to inhibit the adsorption
of chloride at the electrode surface. Al-Salman successfully prepared Zn
nanowires by electrodeposition from 0.05 M ZnCl2/EMIM-TFSI solution
with SiCl4 additive. In brief contrast, the Zn deposits are agglomerates
of 100–200 nm hexagonal platelets in the absence of SiCl4. In future
works, more effective additives and increased understandings on how
additives affect the metal deposition processes are waiting to be high-
lighted.
Due to the large size of ionic species, the viscosity of ILs is typically
1–3 orders of magnitude higher than conventional solvents, which will
lower their ionic conductivity [177]. One way to alleviate this problem
is to include oxygen in the alkyl chain of an IL or to incorporate low
viscosity solvents as diluents to lower the viscosity, such as water [173].
However, the addition of water to the solution decreases the electro-
chemical window of both ionic liquids and shifts the reduction of Zn2+
to less negative values. Therefore, the compatible dilute solvents with
H. Li, et al.
Fig. 28. SEM images (a,b,d,e) and XRD patterns (c,f) of Zn films on gold obtained from 0.1 M Zn(TfO)2 in [EMIm]TfO (a–c) and with 0.015 M Ni(TfO)2 (d–f) at
−1.7 V for 2 h. Reproduced with permission [175]. Copyright 2016, Wiley-VCH.
low viscosity and wide electrochemical stability window remain to be
explored, such as organic carbonates that are widely used in lithium ion
batteries.
The Zn anode in the organic solvents shows a good thermally dy-
namic stability. Therefore, the application of organic solvents is also a
promising solution to minimize side-reactions, resulting in high cou-
lombic efficiency and dendrite-free Zn plating/stripping. Burrell and co-
workers examined the electrochemical, structural and transport prop-
erties of Zn anode using organic solvents for non-aqueous electrolyte
[178]. They found that the acetonitrile (AN)-Zn(TFSI)2, AN- Zn
(CF3SO3)2, propylene carbonate (PC)–Zn(TFSI)2 electrolytes can both
achieve highly reversible Zn plating/stripping behavior with high
Coulombic efficiency > 99%, and provide wide electrochemical
window to ∼3.8 V vs. Zn/Zn2+. Wang's group demonstrated that the
Zn plating/stripping can stably works over 3000 h with a high Cou-
lombic efficiency of 99.68% in Zn(CF3SO3)2 electrolyte using triethyl
phosphate (TEP) as a solvent and co-solvent with aqueous electrolytes
[179]. The enhanced stability and Coulombic efficiency of Zn elec-
trodes is attributed to the highly porous deposits resulting from simple
Zn-deposition/stripping chemistry in both non-aqueous and hybrid
electrolytes. Nazar and co-workers compared the electrochemical be-
havior of Zn/V3O7⋅H2O battery using 1 M ZnSO4 aqueous solution and
0.25 M Zn(CF3SO3)2-AN electrolyte [52]. The battery delivers high ca-
pacity of 375 mA h⋅g−1 at 1C and 275 mA h⋅g−1 even at 8C in aqueous
electrolyte. Whereas, it shows low specific capacity and poor rate per-
formance in organic electrolyte. They conclude that solid solution be-
havior related to Zn2+ ion diffusion within a water monolayer in the
interlayer gap in both systems, but very sluggish interfacial charge
transfer in the organic electrolyte.
5.4. Hydrogel or gel electrolytes
The replacement of liquid electrolyte with solid electrolyte to pre-
pare solid state RZBs can boost their applications in flexible energy
storage for powering various flexible and wearable electronic devices.
The key towards high-performance solid-state RZBs lies on highly
conductive solid-state electrolyte. Conventionally, solid polymer elec-
trolyte formed by suitable complexation of a zinc salt within a polymer
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Nano Energy 62 (2019) 550–587
matrix have been reported, such as poly (ethylene oxide) (PEO)–ZnX2
complexes (X = Cl, Br, I, ClO4, and CF3SO3) [156], poly (vinylidene
fluoride) (PVDF)/PEO-Zn(CF3SO3)2 [180], etc. Unfortunately, the
principle problem with above reported solid polymer electrolytes is
their low ionic conductivity of only 10−5-10−6 S cm−1, which are in-
sufficient for RZBs applications. Furthermore, the solubility of zinc salts
is small and the adhesion between the polymer electrolyte and the
electrode is poor, which lead to high interfacial resistance.
Polymer gel or hydrogel electrolyte swollen with nonaqueous or
aqueous liquid electrolyte offers much higher ionic conductivity of
10−4-10−3 S cm−1, which is acceptable for RZBs. By using gel or hy-
drogel electrolyte, problems associated with conventional liquid elec-
trolytes such as electrolyte leakage, dendrite formation induced safety
concerns can also be avoided. Diverse polymers, such as PEO, PVDF,
poly-(ethylene glycol) (PEG) have been studied as polymer matrix
[181]. The uptake solvents for gel electrolyte includes organic solvents
(e.g., propylene carbonate (PC), ethylene carbonate (EC), ethylene
carbonate (DEC), etc), oligomeric polyethers, ionic liquids while water
is used as solvents for hydrogel electrolyte.
Compared with organic carbonates that are easily volatile, oligo-
meric polyethers such as poly(ethylene glycol) dimethyl ethers
(PEGDMEs) has a lower vapor pressure and high boiling point
of > 300 °C, making them more favorable for open systems such as
secondary zinc air systems. Moreover, PEGDMEs possess unusually
strong capabilities for dissolving large amounts of zinc salts that are an
order of magnitude higher than PC. Xu revealed that zinc salts with a
very large anion, such as Zn(TFSI)2, lead to not only high solubility in
PEGDME, but also high ionic conductivity [182]. Incorporation of a
small amount of EC into PEGDME gives rise to surprisingly large ben-
eficial effects in terms of zinc salt solubility, ionic conductivity and
other electrochemical properties without affecting the volatility of the
electrolyte system. Zinc electrolyte solutions based on these solvents
blend well with poly(vinylidene fluoride-co-hexafluoropropylene)
(PVDF-HFP), leading to gel electrolyte membranes with a high ionic
conductivity of 10−4 S cm−1.
Gel electrolytes based on ionic liquids are also reported due their
wide electrochemical window, high ionic conductivity, high thermal
stability, non-volatility and non-flammability properties. Romero
H. Li, et al.
reported a PVDF-HFP and TFSI-ionic liquids-based gel polymer elec-
trolyte, with and without Zn(CF3SO3)2 salt [183]. Three different ionic
liquids, 1-ethylpyridinium bis(trifluoromethylsulfonyl)imide (EPy
TFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
(EMIM TFSI), and trihexyltetradecylphosphonium bis(tri-
fluoromethylsulfonyl)imide (P6,6,6,14 TFSI), with the same anion,
TFSI−, were added to the host polymer PVdF-HFP. From the impedance
results, a P6,6,6,14 TFSI electrolyte proved to be more resistive than
EMIM TFSI and EPy TFSI based electrolytes, which can be attributed to
the major volume of P6,6,6,14+ cation. Also, the incorporation of Zn
(CF3SO3)2 salt inside the film increased the ionic conductivity for all gel
electrolytes, which can be related to the existence of free triflate anions.
Among the prepared gel electrolytes, the PVDF-HFP + EMIM
TFSI + Zn(CF3SO3)2 membrane exhibits a maximum ionic conductivity
value of 1.73 × 10−1 S m−1, together with low activation energy value,
and a highly reversible and high current density voltammetric behavior.
Since most of the current reported RZBs are using aqueous solution
as electrolyte, the development of hydrogel electrolyte is of pivotal
importance for flexible and solid state RZBs. The use of polyvinyl al-
cohol (PVA) based gel electrolyte, such as PVA/LiCl–ZnCl2–MnSO4
[184], PVA-KCl-Zn(CH3COO)2 [80], PVA-KOH-ZnO [185,186], and
PVA-KOH-ZnSO4 [187] were widely reported for flexible RZBs. For
example, Liu constructed a flexible quasi-solid-state Ni–Zn battery with
PVA-KOH-ZnO alkaline electrolyte [185]. In the cell, ZnO nanoparticles
and NiO nanoflakes are conformably deposited on a 3D hierarchical
carbon cloth-carbon nanofiber (CC-CF) substrate and are used as the
anode (CC-CF@ZnO) and cathode (CC-CF@NiO), respectively. The
polymer electrolyte was prepared by dissolving 2.125 g PVA into
15 mL H2O at 85 °C and then mixed with 10 mL ZnO saturated 6 m KOH
solution. The as-assembled quasi-solid-state Ni–Zn battery achieves an
energy density of 323.3 Wh kg−1 (7.76 mWh cm−3), together with a
peak power density of 8.66 kW kg−1 (0.21 W cm−3) at 172.8 Wh kg−1
(4.15 mWh cm−3). Furthermore, flexible yarn-shaped Ni–Zn battery
with a high output voltage of ∼1.8 V was assembled using PVA-KOH-
ZnSO4 hydrogel electrolyte, which is prepared by dissolving 2 M KOH,
0.08 M ZnSO4∙7H2O and 6 g PVA powder into distilled water with
continuous stirring and heating [187]. The anode of the battery is a 3D
lithium doped TiO2 nanotube-array fiber-shaped electrode (Li-RTiO2),
which, compared to TiO2, exhibits enhanced electrochemical perfor-
mance towards Zn deposition and dissolution during charge/discharge
process due to the introduction of Li dopants. When coupled with Mn-
NiOx cathode that are in-situ electrodeposited on Cu fiber, the full cell
shows the maximum volumetric energy density of 0.034 Wh cm−3 and
power density of 17.5 W cm−3 together with about 95% capacity re-
tention after 20,000 cycles.
Apart from PVA based hydrogel electrolyte, Zhi's group successfully
developed a gelatin and polyacrylamide (PAM) based hydrogel elec-
trolytes for flexible rechargeable Zn–MnO2 batteries, which offers su-
perior flexibility, high water-retention capacity and most importantly
high ionic conductivity of 1.76 × 10−2 S cm−1 at room temperature
[38]. The hierarchical polymer electrolyte (HPE) is synthesized by
grafting PAM onto gelatin chains that are filled in the network of a
polyacrylonitrile (PAN) electrospun fiber membrane (Fig. 29). The
grafting of PAM onto a gelatin hydrogel (gelatin-g-PAM) significantly
enhances the mechanical strength and ionic conductivity of the gel
electrolyte film, and the PAN fiber membrane efficiently reduces the
possibility of a battery short circuit in addition to further improving the
strength of gel electrolyte.
Besides, they also developed a cross-linked PAM based hydrogel
electrolyte, showing good tensile strength (273 kPa), high stretchability
up to 3000% strain as well as a high ionic conductivity of
1.73 × 10−2 S cm−1 at room temperature [188]. Most recently, Li
et al., reported a flexible solid-state Zn/MoS2 battery based on starch/
PAM-hydrogel electrolyte, which is fabricated by grafting super-
absorbent PAM onto starch chains by a solution polymerization tech-
nique [86]. The as-prepared starch/PAM based polymer electrolyte
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Nano Energy 62 (2019) 550–587
exhibits a high ionic conductivity of 2.65 × 10−2 S cm−1, which is
impressively high in comparison with other Zn ion conducting polymer
electrolytes.
Furthermore, Zhi's group found a new electrolyte comprising so-
dium polyacrylate (PANa) hydrogel, which enables an order of mag-
nitude higher cycling stability than state-of-the-art counterparts and
high capacities for the quasi-solid-state alkaline Zn batteries [189]. The
PANa was synthesized by polymerization of acrylic acid (AA) mono-
mers neutralized by NaOH in the presence of ammonium persulfate
(APS) initiator. Then the PANa was soaked with 0.2 M Zn(CH3COO)2
and 6 M KOH to obtain the hydrogel electrolyte. The PANa is a well-
known superabsorbent polymer, which can absorb water as much as
200–300 times of its own weight. It is worth noting that the water
adsorption and retention capability of PANa is much better than other
hydrogels such as PVA, PAM and PAA. In addition, PANa hydrogel can
keep decent mechanical properties even when it is saturated with
highly concentrated solutions, which is important as an electrolyte for
flexible energy storage devices.
By adding Fe3+ as cross-linkers during the polymerization process
of PANa, Huang et al. successfully prepared Fe3+ cross-linking PANa
hydrogel, which has self-healing ability. This is because the Fe3+ cross-
linkers form ionic bonds in and between the PANa chains, thus re-
connecting the broken network. As a result, this Zn–NiCo battery with
this hydrogel electrolyte can be autonomically self-healed with over
87% of capacity retained after 4 cycles of breaking/healing. Cui re-
ported a smart flexible RZBs with cooling recovery ability by utilizing a
temperature-sensitive sol–gel transition behavior of the thermo-re-
versible poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene
oxide) (PEO-PPO-PEO, Pluronic) polymer hydrogel electrolyte (Fig. 30)
[67]. When this battery system was exposed to extreme deformations, a
simple cooling process can repair the fractured electrode-electrolyte
interface, thus enabling in situ restoration of the electrochemical per-
formance (healing efficiency up to 98% with a fast recovering time of
5 min).
In summary, electrochemical behaviors of the Zn2+ ions in different
types of electrolytes including neutral or mildly acidic, alkaline, aqu-
eous-based hydrogel or gel-type, ionic liquid and organic electrolytes.
The comparison of these electrolytes can be summarized in Table 3.
6. Rechargeable zinc batteries with advanced features
Although several efforts have been spent for fundamental innova-
tions of RZBs, it is still hard to satisfy the requirements of various
practical applications, like wearable/flexible demand, safety require-
ments, self-healing function, weavability and smart switch, etc.
Recently, intensive research efforts focus on new features of RZBs.
These RZBs exhibit extreme safety properties, weaveable, printable,
self-healing, smart switch properties and response to external light,
which integrates techniques from multiple disciplines, such textile,
optics, 3D print and polymer, etc. In the following sections, RZBs with
these advanced features are discussed.
6.1. Wearable/flexible zinc-based batteries
The increasing demand of power supply for portable and wearable
electronics (such as Apple watch, smart wristband, virtual reality hel-
mets, etc.) propels the development of flexible/wearable batteries.
Notably, replacing aprotic energy storage devices such as LIBs with
aqueous RZBs represents a great leap for wearable and implantable
electronics applications. It is due to the fact that LIBs suffer from in-
trinsic cost and safety issues, especially when they are used in wear-
able/implantable devices in close contact with human body. In fact,
safety issues are much more severe for flexible and wearable batteries
than well-packaged rigid ones, since they are liable to experience more
mechanical impacts and damages during daily use, including being
bent, folded, stretched, hit, or even soaked in water. Aqueous batteries
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 29. (a) Schematic illustration for the synthesis of HPE. (b) Photograph of HPE showing high flexibility. (c) SEM image of the HPE film (top view). (d) SEM image
of the HPE film (cross-section). (e) FTIR spectra of gelatin-based electrolyte and HPE. (g) AC impedance spectra of gelatin-based electrolyte and HPE. Scale bars,
1 cm (b), 10 μm (c), 20 μm (d). Reproduced with permission [38]. Copyright 2018, The Royal Society of Chemistry.

can stably operate under these complicated environments, which can
solve the intrinsic safety and fabrication issues of flexible aprotic bat-
teries. Besides, aqueous batteries offer other unique features such as
eco-friendliness, low cost, and ease of fabrication, which enable them as
competitive candidates for flexible and wearable applications [190].
The next-generation of wearable batteries could be worn like clothes
and meanwhile shows sufficient adaption of dynamically curved body.
Furthermore, ideally, the batteries could be integrated in textile like
fabrics of clothes. For example, Zhi's group developed yarn-based
weavable NiCo/Zn battery, which could be knitted as wristband to
power various electronic devices (Fig. 31a) [191]. The yarn consists of
stainless steel 316L and the yarns can be further weaved or knitted to
clothes. Thus, yarn batteries are promising in weaveable and knittable
batteries. The wearable NiCo/Zn battery was fabricated by uniform
electrodeposition of nickel cobalt hydroxide and Zn on conductive yarn-
based fabrics. Due to the highly conductive yarn-based fabrics and high-
performance nickel cobalt hydroxide, the yarn-based batteries ex-
hibited high specific capacity of 5 mA h cm−3, energy densities of
8 mWh cm−3, and power densities of 2.2 W cm−3. Furthermore, the
battery showed ultrahigh rate capability of 116C. Lee's group developed
a stretchable Zn–Ag battery based in nanowire elastic conductors [192].
The Ag electrode was fabricated by lithographic filtration method,
which simultaneously offer active materials and current collector
(Fig. 31b). The battery can be stretched up to 80% and meanwhile
maintains their functionalities even in this highly stretched state. In
addition, Ana Claudia Arias's group presented a mechanically robust,
intrinsically Zn–Ag batteries based on helical band springs (Fig. 31c).
The serpentine-like Zn–Ag batteries could be stretched with tunable

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H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 30. (a) The cooling-recovery function by incorporation of a thermo-reversible pluronic hydrogel electrolyte (PHE). (b) Photographs of PHE and its polymer chain
configurations (insets) at −5 °C and 25 °C. (d, e) The wetting behavior of Zn electrode surface with PHE during evolution of cooling time (−5 °C). (c, f) Cross-
sectional SEM images of c) the blank Zn electrode and f) the Zn electrode fully wetted by PHE. Reproduced with permission [62]. Copyright 2017, Wiley-VCH.

degree and directionality without specific capacity loss. Furthermore,
the fiber-shaped battery is integrated with a photovoltaic module, re-
sulting in the rechargeability of the battery by solar energy [193].
The aqueous Zn–MnO2 battery characterized by low cost, good
safety, eco-friendliness and high output voltage is significantly pro-
mising for wearable/flexible electrochemical energy storage devices.
However, conventional aqueous Zn–MnO2 battery suffers from sharp
capacity decay, large resistance, inferior capacity and rate capacity due
to utilization of Zn foil/paste and binder. Lu's group construct a flexible
quasi-solid-state rechargeable Zn–MnO2@PEDOT battery (Fig. 31d),
where the MnO2@PEDOT and metal Zn are directly grown on flexible
substrate of carbon fiber cloth without any binder [194]. The PEDOT
acts as a buffer layer to suppress the structural pulverization. The de-
veloped electrodes are assembled with polymer electrode to construct

Table 3
Comparison of various electrolytes that used in RZBs.

581
H. Li, et al.
Fig. 31. (a) weaveable yarn-based Zn–NiCo battery. Reproduced with permission [191]. Copyright 2017, American Chemical Society. (b–c) stretchable Zn–Ag
battery. Reproduced with permission [192,193]. Copyright 2014, Wiley-VCH. (d) Photos of 45 light-emitting diodes and an electric watch lighted by quasi-solid-state
Zn–MnO2@PEDOT batteries. Reproduced with permission [194]. Copyright 2018, The Royal Society of Chemistry. (e) Zn–MnO2 batteries with extremely safe
properties: bending, hammering combustion, soaking, washing, weight loading, drilling and sewing test. Reproduced with permission [38]. Copyright 2018, The
Royal Society of Chemistry.
quasi-solid-state devices. It exhibits an excellent capacity of 282.4 mA h
g−1, great charge/discharge cycling stability and a remarkable energy
density of 504.9 Wh kg−1. Furthermore, three batteries connected in
series can power 45 light-emitting diodes and it can be pasted onto
clothes as a wearable supply power to illuminate a wristwatch.
As for wearable battery, it is likely to experience various mechanical
impact. Thus, it should satisfy the requirement of various working
conditions. The wearable battery should possess impressive safe per-
formance including bending, hammering, combusting, washing,
weight-loading, drilling and sewing without damage or harm to users.
Zhi's group developed an extremely safe and wearable Zn-ion battery
based on hierarchical structured polymer electrolyte [38]. The hier-
archical polymer electrolyte (HPE) was fabricated by grafting poly-
acrylamide (PAM) onto gelatin chains filled in polyacrylonitrile (PAN)
electrospun fiber membrane. The HPE not only efficiently reduces the
possibility of battery short circuit but also shows highly mechanical
strength. Employing the HPE as polyelectrolyte, deposited Zn as anode
and a-MnO2 nanorod/carbon nanotubes composite as cathode, the
solid-state Zn-ion batteries were constructed. It shows excellent safety
and wearability, demonstrating the ability to work under a number of
severe conditions including being cut, bent, hammered, punctured, put
on fire, sewed using a commercial sewing machine and even washed
with water for almost 30 min without any packaging (Fig. 31e). Fur-
thermore, a waterproof, tailorable yarn Zn-ion battery was developed
based on double-helix yarn electrodes and a cross-linked PAM electro-
lyte [188]. It exhibits superior knittability, stretchability (300% tensile
elongation) and waterproof capability. Even soaking underwater for
12 h, its capacity can maintain 96.5%. It shows immerse potential as
energy storage devices for wearable application.
6.2. Rechargeable zinc-based batteries with other advanced features
Flexible batteries are promising for wearable and portable electro-
nics, such as flexible displays, wearable sensors and smart phones. The
solid-state battery consists of anode, polyelectrolyte and cathode. One
can endow polyelectrolyte with new functions or new fabrication
methods of electrode materials to develop multifunctional batteries.
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Nano Energy 62 (2019) 550–587
Although only a few works reported about Zn-ion batteries with new
function or features by modifying polyelectrolyte or special fabrication
of electrodes, it is the direction of wearable batteries for integration and
miniaturization.
The batteries are inevitable to be damaged in actual use. Inspired by
human bones, the damaged parts can be repaired by themselves, self-
healing properties. The endowment of self-healing properties to energy
storage and conversion devices is attractive for functional restoration.
The self-healing in batteries contains both mechanical and electrical
restoration. Batteries are typically comprised of two electrodes and
polyelectrolyte. The mechanical performance can be restored by poly-
electrolyte, while the electrical performance is restored by electrodes
alignment. Thus, the development of self-healing polyelectrolyte is
critical for self-healing battery. A self-healing polyelectrolyte of sodium
polyacrylate hydrogel chains crosslinked by ferric ions is exploited to
promote dynamic reconstruction of an integral network [189]. PANa is
the hydrogel electrolyte matrix, owing to its high compatibility with
sufficient electrolyte ions for ion transportation and the Fe3+ cross-
linkers provide ionic bonding among PANa chains. Employing the as-
synthesized PANa-Fe3+ as polyelectrolyte, the NiCo/Zn battery main-
tains typical charge-discharge plateaus and 87% capacity after for
cutting-healing cycles (Fig. 32a). The self-healable Zn-based batteries
are particularly promising for the low-cost and highly efficient wear-
able electronics.
Apart from that, Wang et al. assembled flexible Zn-ion battery with
wire shape configuration and shape memory function using gelatin-
borax hydrogel as electrolyte and utilizing conductive yarn combined
with Nitinol shape memory wire as electrode substrate [195]. The
shape memory function enables the battery to restore original shape
and initial energy storage capability just through temperature trigger
(Fig. 32b). The specific mechanic properties of the Nitinol wire endow
the wire-shaped battery deformation recovery capability. The de-
formation can be effectively recovered to initial state just by immersing
the device in 45 °C water and their electrochemical performance can be
maintained in this process. Furthermore, the flexible shape-memory Zn-
ion battery shows good stability of mechanical and electrochemical
performance against 5 bending-recovery cycles.
H. Li, et al. Nano Energy 62 (2019) 550–587

Fig. 32. (a) A self-healable Zn–NiCo battery. Reproduced with permission [189]. Copyright 2018, Wiley-VCH. (b) Discharge capacity and capacity retention of shape-
memory Zn–MnO2 battery. Reproduced with permission [195]. Copyright 2018, The Royal Society of Chemistry. (c) Micro Zn-ion batteries as a color filter in a
screen. Reproduced with permission [86]. Copyright 2018, The Royal Society of Chemistry. (d) Cooling-recovery smart Zn–MnO2 battery. Reproduced with per-
mission [196]. Copyright 2018, Elsevier. (e) Printable Zn-ion battery. Reproduced with permission [197]. Copyright 2018, Wiley-VCH.

Zhi's group developed a battery-in-screen configuration of photo-
luminescent microbatteries embedded in color filter of screen by em-
bedding colloidal CdTe quantum dots into polyelectrolyte [86]. The
water soluble green or red light emitting CdTe quantum dots were
combined with the blue-emitting gelatin-based polyelectrolyte. Then, a
semitransparent aqueous Zn-MnOx/polypyrrole microbattery is con-
structed utilizing synthesized polyelectrolyte containing CdTe quantum
dots. As shown in Fig. 32c, the battery arrays can function simulta-
neously as the color filter emitting in three primary RGB colors, and a
power supply for the full-color display.
In addition, a reversible sol-gel transition polyelectrolyte of poly (N-
isopropylacrylamide-co-Acrylic acid) (PNA) with changes of tempera-
ture is developed for thermal self-protection batteries. As shown in
Figure 32d, the Zn-ions can well work, owing to the sol state of the PNA
polyelectrolyte at low temperature. Whereas, the polyelectrolyte
changes to stationary hydrogel up to a certain temperature, leading to
the inhibition of the diffusion of Zn ions, thus resulting in shutting
down batteries [196]. This work provides a smart and active strategy to
achieve dynamic and reversible self-protection.
The application of printing technologies can be convenient and
scale-up for battery construction, where the electrode active materials
are simply painted or casted on substrates. Somenath Mitra's group
developed a printable, flexible nickel-Zn battery by painting the inks of
metal oxide incorporated into carbon nanotube to flexible substrate
(Figure 32e) [197]. The carbon nanotube-metal oxide inks were syn-
thesized by simply precipitative techniques, which shows high elec-
trical conductivity. The fabricated batteries exhibit good performance
even under bending conditions and the overall technologies are scalable
by printing methods. It shows good prospect of developing flexible/
wearable batteries on a large scale.
A rechargeable battery with both flexibility and electrochromism
integrated into a single apparatus is a major component for smart
flexible electronics. Huang et al. realized a flexible, electrochromic and
rechargeable battery by successfully matching electrochromic poly-
pyrrole (PPy, as cathode) with zinc (Zn, as anode) [80]. The fabricated
rechargeable Zn//PPy battery delivers a high capacity of 123 mA h
gppy−1. It possesses flexibility and an electrochromic capability of
turning from black to yellow when the voltage changes from 1.2 to 0 V.
In addition, the battery exhibits a unique function of a short circuit
chromatic warning which turns yellow at 0 V. The battery, uniquely
combined with these multiple smart features, represents solid progress
in smart flexible electronics.
7. Summary and perspectives
In this review, we introduce the unique characteristics of re-
chargeable Zn-based batteries. An essential overview is presented, in-
cluding the fundamental chemistry of different RZB systems, Zn anode
and cathode materials as well as electrolytes based on different che-
mistries. Various optimization strategies aiming at achieving high-
performance aqueous RZBs was analyzed. In addition, the development
of RZBs with different features in the last few years are summarized.
The development of RZBs can be briefly summarized as:
(1) Different energy storage mechanisms have been demonstrated in
aqueous RZBs, which includes: Zn2+ intercalation/deintercalation
mechanism, co-insertion mechanism, conversion reaction me-
chanism, hybrid chemistry mechanism and Zn-air mechanism.

583
H. Li, et al.
Based on these different chemistries, various cathode materials
(e.g., Mn-based, V-based, Li-based, Na-based, Ni-based, and Co-
based, Prussian blue analog based and organic materials) and dif-
ferent kinds of electrolytes (neutral or mildly acidic, alkaline,
polymer and ionic liquid-based electrolytes) have been investigated
for RZBs.
(2) Structural water and “pillar” effect of the intercalated metal ions
(e.g., Li+, Na+, Ca2+, Zn2+, Mg2+) in the interlayers as well as
structural defects (e.g., oxygen vacancy, phase boundary, highly
active facets) play a vital role in enhancing the structural stability
and electrochemical performance of cathode materials for RZBs.
(3) Introducing additives, surface coating and optimizing the structural
design of Zn anode have been demonstrated to be feasible strategies
to mitigating the issue of zinc electrodes (e.g., zinc dendrite, shape
change, corrosion and passivation)
(4) “Water-in-salt” type and polymer (e.g., hydrogel) electrolytes pro-
vide a new opportunity to enhance the reversibility of the Zn anode
in aqueous electrolytes and achieve better electrochemical perfor-
mance for RZBs.
Besides these achievements discussed in this review, there is still
much scope for the further development of high-performance RZBs. The
potential future research directions as well as the challenges should be
addressed are summarized as follows:
1. Fundamental mechanisms about the electrochemical reactions for
RZBs should be further elucidated, especially for Mn-based cathodes. As
we have discussed above, the Zn2+ storage mechanisms of Mn-based
materials are controversial and under debate. The lack of rigorous
protocols and standard characterization techniques may lead to the
ambiguous interpretation, which hinders the better design and in-
vestigation of high-performance electrodes and electrolytes for RZBs.
Developing and using multiple electrochemical approaches and more
advanced characterization techniques as well as precise theoretical
calculations are urgently needed for tackling this challenge.
2. As aqueous energy storage systems, RZBs suffer from the low
operating voltage (generally lower than 1.8 V) due to the narrow stable
working window of aqueous electrolytes. Recent advances demonstrate
that “water-in-salt” electrolytes can effectively extend the operating
voltage of aqueous battery beyond 1.8 V, opening new direction for the
design of high voltage and high energy density RZBs. However, such
unprecedented improvements were achieved with very expensive Li
salts such as lithium bis(trifluoromethane sulfonyl)imide (LiTFSI),
which greatly limit its wide application. Developing novel hydrogel or
“water-in-salt” electrolytes with the ability to suppress the electrolysis
of water may be a promising direction to increase the operation voltage
and energy density of the device.
3. Since the stability of electrodes and electrochemistry perfor-
mances of the RZBs are closely associated with the characteristics of the
electrolyte to which it is exposed, many efforts should be focused on the
development of high-performance electrolytes. In general, the aqueous
based electrolyte (including mildly acid and alkaline electrolytes) are
preferred because they are environmentally benign and cheaper and
have much higher ionic conductivity. But the hydrogen evolution, low
stability window is still an issue to overcome. Thus, novel additives for
electrolytes which can provide high electrochemical stability, reversible
Zn plating/stripping and better cycle stability of cathode materials, is
still highly desirable. As an alternative approach, the development of
non-aqueous electrolytes for RZBs may be an option. Besides, other
novel-type electrolytes such as “water-in-salt”, hydrate-melt and hy-
drogel electrolytes hold great potential for future development of high-
performance RZBs.
4. Developing high-performance cathode materials that possess both
high capacity and superior structure stability during the long-term cy-
cling process remain a huge challenge. With coordinated water mole-
cules, the hydrated Zn2+ (i.e., [Zn(H2O)6]2+) and H+ (i.e., H3O+)
exhibit strong electrostatic interaction with the host lattice. The crystal
584
Nano Energy 62 (2019) 550–587
structure of electrodes is more likely to collapse due to the repeated
intercalation/deintercalation of hydrated Zn2+ and H+ (i.e., H3O+),
leading to a rapid capacity fading upon cycling. Besides, the dissolution
of cathode materials (especially the Mn-based and V-based materials)
into the electrolytes can also occur upon electrochemical operations,
which is harmful for the cycling life of RZBs. Previous reports demon-
strate that Zn(CF3SO3)2 can mitigate the dissolution of cathode mate-
rials and the pre-added Mn2+ ions into the electrolyte and the inter-
calated metal ions into the interlayers may enhance the cycling
stability. However, these approaches do not address the issues of low
stability and capacity fading very well. Therefore, more effective stra-
tegies in terms of structural engineering (e.g., oxygen vacancies, ion
doping) of the existing materials and exploring new cathode materials
should be further investigated. Besides, based on the hybrid chemistry
mechanism and the high reversibility of Zn electrode in aqueous elec-
trolyte, coupling Zn anode with other ion-intercalated materials (such
as Li+ and Na+) to construct high-performance hybrid battery systems
is an attractive research direction.
5. The main issues of Zn anode such as zinc dendritic, corrosion, low
Columbic efficiency, and shape change still hinder the development of
the Zn anode. These problems are much severe at high current den-
sities. Many efforts have been devoted to optimizing the electrolyte and
Zn electrode to tackle these issues, which include introducing additives,
surface coating and structure design (high surface area/3D electrode).
However, there is no any unique solution to overcome all issue of Zn
anode to the ground, especially in alkaline electrolytes. Designing na-
nostructured or high-surface-area Zn-based materials with multi-di-
mensional or hierarchical architecture coupling with additives or sur-
face modification may be an effective way to enhance the performance
of Zn electrodes.
6. Developing flexible/wearable and multifunctional RZBs that in-
corporate new features and smart functions such as self-healing, self-
protection, stretchability, photodetection, shape-memory, and thermal
response, represents a very promising direction and hold great potential
for next-generation electronic products. One of the main challenges is
how to fabricate solid-state or quasi-solid-state polymer-based electro-
lytes that possess high ionic conductivity, good mechanical strength
and multiple functionalities (e.g., stretchability, compressibility,
toughness and self-healing ability). Apart from that, device optimiza-
tion or other smart designs should be considered to enhance the com-
patibility between the incorporated multifunctional electrolytes and
smart materials as well as other components in the battery, aiming at
developing multifunctional devices without significantly sacrificing
electrochemical performance. Furthermore, by applying other smart
materials and rational design inspired from natural sophisticated sys-
tems, the prototypes of flexible/wearable and multifunctional RZBs
could be greatly enriched.
Acknowledgements
This research was supported by GRF under Project
N_CityU11305218. The work was also partially sponsored by the
Science Technology and Innovation Committee of Shenzhen
Municipality (the Grant No. JCYJ20170818103435068) and a grant
from City University of Hong Kong.
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Hongfei Li obtained his B.S. degree and M.S. degree in
materials science and engineering from Central South
University and Tsinghua University, respectively. After
that, He received his Ph.D. degree from City University of
Hong Kong under the supervision of Prof. Chunyi Zhi. Now,
he is an assistant professor at Songshan Lake Materials
Laboratory. His research focuses on flexible and wearable
energy storage devices, aqueous batteries and polymer
electrolytes.
H. Li, et al.
Longtao Ma received his B.S. degree in materials science
and engineering from China University of Geosciences
(Wuhan) in 2014 and got his M.S. degree in materials sci-
ence from Northwestern Polytechnical University in 2017.
Currently, he is a Ph.D. candidate under supervision of Prof.
Chunyi Zhi at City University of Hong Kong. His research
interests mainly focus on flexible/wearable energy con-
version and storage devices, including zinc-air/ion batteries
and hybrid batteries.
Cuiping Han received her B.S. degree from China
University of Petroleum (Huadong) in 2010 and Ph.D. de-
gree from Tsinghua University in 2015 with Prof. Baohua
Li. She visited Georgia Institute of Technology during
2014–2015 as a visiting scholar. Then she worked as a
postdoc with Prof. Ching-Ping Wong at Chinese University
of Hong Kong under the support of Xiangjiang scholar
program during 2015–2017. Now she is a research associate
at Shenzhen University. Her research is focused on elec-
trode materials for lithium-ion batteries and super-
capacitors and Zn batteries.
Zifeng Wang received his B.Eng. degree from the Institute
of Powder Metallurgy, Central South University in 2013
and then received his M.Sc. degree from the Department of
Physics and Materials Science, City University of Hong
Kong, in 2014. He got his Ph.D. degree from the
Department of Materials Science & Engineering, City
University of Hong Kong. His research focuses on the flex-
ible energy storage devices with aqueous or hydrogel
electrolytes.
587
Nano Energy 62 (2019) 550–587
Zhuoxin Liu received his B.S. degree in polymer science
and engineering and M.S. degree in materials science from
Sichuan University, Chengdu, China, in 2012 and 2015,
respectively. He is now a Ph.D. candidate under the su-
pervision of Prof. Chunyi Zhi at City University of Hong
Kong, China. His present research interests mainly focus on
flexible energy storage devices, including aqueous lithium-
ion batteries and supercapacitors.
Zijie Tang is a PhD student in the Department of Materials
Science and Engineering, City University of Hong Kong. He
received his Bachelor degree from the School of Materials
Science and Engineering, Central South University. His re-
search mainly focuses on high-performance zinc-ion battery
electrodes and polymer electrolytes for wearable energy
storage devices.
Chunyi Zhi is currently an associate professor in the
Department of Materials Science and Engineering, City
University of Hong Kong. He received his PhD degree in
physics from the Institute of Physics, Chinese Academy of
Sciences. Then he moved to National Institute for Materials
Science (NIMS) in Japan as a post-doctoral fellow, followed
by an ICYS research fellow, researcher (faculty) and senior
researcher (permanent). His research focuses on wearable/
flexible energy storage devices and aqueous electrolyte
batteries.