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Catalysis Today 445 (2025) 115108
Contents lists available at ScienceDirect
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
Chemistry in rechargeable zinc-air battery: A mechanistic overview

Arkaj Singh , Ravinder Sharma , Akriti Gautam , Bhavnish Kumar , Sneha Mittal , Aditi Halder *
School of Chemical Sciences, Indian Institute of Technology Mandi, Himachal Pradesh 175005, India
A R T I C L E I N F O A B S T R A C T
Keywords: The progress in civilization can be related to the development of newer technological development and asso
Zinc-air battery ciated energy demand to run those systems. The personalized healthcare systems, the depletion of conventional
eg orbital occupancy fossil fuel reserve led us to think about alternative energy storage devices. Thus, it is important to develop energy
Bifunctional oxygen electrocatalyst
storage materials with the property of good mechanical strength and stability for longer hours. Zn-air batteries
Gel polymer electrolyte
Photo-rechargeable battery
(ZAB) show the promises to be an alternative of Li-air batteries for this purpose. ZABs can fulfill our need of
Anode modification stringent requirements such as high energy density, cost-effectiveness and it is safer as compared to Li-ion
batteries. The stability of zinc in aqueous and air environments makes ZAB technology more reliable and
effective for small to large-scale flexible electronics. To further enhance its efficiency, different scientific ma
terials and methods have been developed over decades, of which this review provides detailed insight into the
parameters and mechanisms related to the key components of the ZAB for enhancing the performance of ZAB. We
summarized the working mechanism of overall reversible-ZABs and then independently we explained the
mechanism and problems associated with cathode, anode, and electrolyte, followed by the current breakthrough
related to each. Aspects such as role of optimal eg occupancy in bifunctional activity, inhibition of zinc dendrite,
and gel polymer electrolytes with enhanced conductivity and strength are specifically highlighted. To facilitate a
broad discussion among different research communities, important scientific hurdles and their potential solution
related to R-ZABs are also summarized.
1. Introduction portable electronic devices. Electric vehicles (EVs) represent a signifi

cant transformation aimed at replacing internal combustion engines,
Transformative innovations in energy generation and utilization signifying an industry wherein batteries may emerge as the modality for
technologies are necessary to ensure a safe and sustainable future. The energy storage. However the economic viability of the EVs among
depletion in fossil fuel reserve and consequent increase in green-house consumers remains not so popular due to the cost and concerning safety
gases in the atmosphere led us to the newer pathways to utilize issues[1,2]. Although, lithium-ion batteries are the most dominating
renewable energy sources like wind, solar, hydroelectric power. How battery technology in the market since 1990s, however disadvantages
ever, the stochastic nature of the renewable energy often creates a associated with the high cost and concerns about the safety due to the
disparity between excess energy generation in the afternoon and inad use of lithium and organic electrolytes made researchers invest towards
equate generation in the evening which of high demand. Similarly, the development of beyond lithium-next generation battery storage
weather conditions also mess around with the uninterrupted power devices[3–5]. The metal–air batteries, are currently attracting great
supply. In those situations, energy storage devices play vital role for interest owing to the complex chemistry of the interrelated electro
supplying current on demand and is important to electrical systems, chemical reactions occurring between metallic electrodes and bifunc
allowing for load leveling and peak shaving, frequency regulation, tional oxygen (O2) electrodes[6–8]. Metals such as potassium (K),
damping energy oscillations, and improving power quality and reli sodium (Na), lithium (Li), magnesium (Mg), iron (Fe), aluminum (Al),
ability. Batteries are type of energy storage devices that can convert and and zinc (Zn) exhibit substantial potential to fabricate noble metal-air
store chemical energy. Batteries have the ability to be scaled down to batteries. Furthermore, the additional advantage associated with the
small sizes, which have given them an additional advantage over direct utilization of air as well as exclusion of oxygen storage part, helps
traditional form of energy storage thereby, making them important for metal-air batteries to attain superior energy density compared to
* Corresponding author.
E-mail address: [email protected] (A. Halder).
https://doi.org/10.1016/j.cattod.2024.115108
Received 29 August 2024; Received in revised form 15 October 2024; Accepted 22 October 2024
Available online 23 October 2024
0920-5861/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
A. Singh et al. Catalysis Today 445 (2025) 115108
existing commercial lithium-ion batteries[9,10].

Among various metal-air batteries, lithium-air batteries are the most
favorite choice due to their ability to deliver large cell voltage and the
highest energy density. However, batteries with alkaline metal anodes
(specifically lithium and potassium) pose significant safety risks when
they are subjected to atmospheric oxygen or aqueous environments[6].
The energy densities associated with Mg and Al air batteries are com
parable to Li-air batteries but due to their low reduction potential
(specifically, magnesium at − 2.372 V and aluminum at − 1.662 V), they
are prone to self-discharge via hydrogen evolution reaction[11]. Due to
their high earth abundance, Zn and Fe are the potential candidate for
metal-air batteries. The higher theoretical energy density and cell
voltage (1086 Whkg− 1and 1.66 V) associated with Zinc-air battery has
received greater attention than Fe-air batteries (the theoretical energy
density and cell voltage of Fe–air batteries are determined to be
763 Wh kg− 1 and 1.28 V, respectively). Interestingly Zinc-air battery is
not a new technology as the first primary zinc-air battery were first
commercialized in 1930[12]. They delivered high volumetric energy Fig. 1. Schematic showing the rechargeable zinc-air battery.
density up to 1400 WhL− 1 and are currently employed in hearing aid
devices, illumination for navigational purposes, and railway signal de back into oxygen which is commonly known as the oxygen evolution
vices[13–15]. Rechargeable zinc-air batteries are also in the limelight process (OER): backward rection of Eqs. 1 and 3. The simplified overall
since 1970, but their commercialization remains an issue. A research reaction form of zinc-air battery is represented in Eq. 4.
attempt has projected the expenditure of approximately US$160 kWh− 1 Reactions at zinc anode
for rechargeable Zn–air batteries employed in electric vehicles[16].
Several other investigations have postulated that the expenses might be Zn + 4OH- ↔ Zn(OH)2- -
4 +2e (E = -1.25 V vs SHE) (1)
reduced to below US$10 kWh− 1, representing a reduction of nearly two Zn(OH)2- ↔ ZnO + H2O + 2OH -
(2)
4
orders of magnitude compared to the Li-ion batterie[17]. As a conse
quence to this, the Zn–air batteries are poised to emerge as a promising Reactions at air cathode
energy storage alternative for many applications, ranging from electric
O2 +2H2O ↔ 4OH- (E = 0.4 V vs SHE) (3)
vehicles, electrical grid management to portable electronic devices.
In spite of having many advantages, the successful commercializa Overall Reaction
tion of Zn-air battery has been impeded due to the slow kinetics of air
cathode, irreversible reactions on the zinc anode, and electrolyte satu 2Zn + O2 ↔ 2ZnO (E = 1.65 V vs SHE) (4)
ration or leakage[18]. In recent years, numerous scholarly review arti
Parasitic reactions
cles reported about the comprehensive details regarding the geometric
configuration and charge storage mechanisms inherent to Zn–air bat Zn + 2H2O → Zn(OH)2 + H2 (5)
teries, alongside the initiatives aimed at enhancing various constituent
components of these batteries[19–21]. The research interest regarding KOH + CO2 → KHCO3 or 2KOH + CO2 → K2CO3 + H2O (6)
Zn–air batteries are developing with considerable speed. In order to According to the reaction mechanism of zinc-air battery (Eqs. 1 and
align with the rapid pace of this research advancement, this review aims 3), the theoretical working voltage of zinc-air battery by coupled redox
to provide an overview of the research undertaken in the preceding five reaction at both the electrodes calculated to be 1.65 V vs standard
years. In this review, we mainly focus on the mechanistic aspects of each hydrogen electrode[24]. This theoretical cell voltage in real-life appli
component of the zinc-air battery. In the first section, we discussed the cation of ZAB is less than 1.2 V while discharging and for charging it is
overall mechanism of rechargeable zinc-air battery followed by few more than 2 V (current density varies from 1 to 10 mA cm− 2. Due to this
methods for the evaluation of the battery. In the next section, we dis large deviation from the theoretical voltage value, the energy efficiency
cussed each component of the battery (cathode, electrolyte, and anode of the majority of rechargeable zinc-air batteries is observed to be below
respectively) with detailed mechanism, factors that affect the perfor 60 %, which can be ascribed to several underlying issues[25].
mance, and recent research articles that show how to improve the bat The following issues affect the efficiency of zinc-air battery-
tery performance by playing with the chemistry of materials. The last
section is totally dedicated to the device fabrication and its types fol 1. Sluggish kinetics of OER/ORR reactions.
lowed by the conclusion. 2. Formation of stable insoluble ZnO.
3. Parasitic reactions like hydrogen evolution reaction (HER) and car
1.1. Working mechanism of overall zinc-air battery bonate formation as shown by Eqs. 5 and 6.
The working principle of a rechargeable zinc-air battery is quite

simple as can be seen from the Fig. 1. Zinc atoms lose electrons during 1.2. Methods to characterize zinc-air battery
the discharge process and the oxidized zinc as zinc ion goes into the
solution where it combines with OH- ions to form soluble zincate ions The basic evaluation parameters for characterizing zinc-air batteries
(Zn(OH)2-4 ) given in the forward reaction of Eq. 1. As the discharge are same as for any other electrically rechargeable battery. A typical
process continues and the concentration of zincate ion in the electrolyte assessment procedure focuses on key performance indicators for the
becomes saturated, zincate ion transforms into insoluble precipitates battery including galvanodynamic polarization, galvanostatic cycling,
(Eq. 2)[22,23]. Generated electrons at the anode reach the cathode via galvanostatic full discharge, and electrochemical impedance spectros
an external circuit where they reduce oxygen to form OH- ions via ox copy[26].
ygen reduction reaction (ORR) as shown in forward reaction of Eq. 3.
During the charging of the ZAB, the Zinc ion from the electrolyte gets 1.2.1. Galvanodynamic polarization
plated at the anode and hydroxide ion by losing four electrons converted The term “galvanodynamic” is used to refer the technique where a
2
current is constantly varied at a certain rate, applied to an electrolyte or 2. Bifunctional oxygen electrocatalyst
electrode. This polarization methodology is used to measure the devia
tion of the battery’s operational voltage from the open-circuit voltage Electrochemical oxygen reduction reaction (ORR) and oxygen evo
(OCV) by applying both discharging and charging currents at steadily lution reaction (OER) are the key reactions that make a metal-air battery
increasing their magnitude. The resultant potential responses are truly rechargeable. To date, the best-known catalyst for OER is RuO2,
recorded as a function of current, producing the discharge and charge and for ORR is Pt/C respectively which suffer from many disadvantages
polarization graphs. The difference between the operational voltage and e.g. high cost, stability in the electrolyte especially at higher oxidation
the OCV (i.e., discharge or charge overpotential) serves as a direct potential[18,27,28].
representation of the cumulative voltage losses attributable to activation
and mass-transfer polarization at each electrode, alongside the Ohmic
2.1. Oxygen evolution reaction
resistance inherent to each element of the electrochemical circuit. The
power density of the zinc–air battery can be graphically represented as a
The recharging process of ZAB involves the oxygen evolution reac
function of current density by multiplying the discharge voltage by the
tion which undergoes 4e- pathways and its general mechanism in
applied current density, thereby allowing the identification of the peak
alkaline electrolyte can be seen in Fig. 2(a). The mechanism starts with
power density.
the adsorption of hydroxyl ions in the vacant metal site by the 1e-
oxidation to form MOH followed by deprotonation from MOH to form
1.2.2. Galvanostatic cycling
MO with the removal of another electron. Nucleophilic attack of another
Electrochemical long-term durability tests for rechargeable zinc air
OH- ion on MO gives MOOH by loss of one electron again followed by
batteries are performed using galvanostatic charge-discharge cycling
proton-coupled electron transfer resulting in the release of O2 and
technique. In galvanostatic charge-discharge technique, fixed positive
generation of free active sites. OER involves multiple intermediates
and negative current is applied alternately for large number of cycles
(MOH, MO, and MOOH) in four reaction steps, and each of these steps
and generated charging and discharging potential is noted. Compared to
can affect the OER performance. Efforts have been made to correlate
the galvanodynamic polarization testing, galvanostatic cycling tech
OER activity with a single descriptor. In the mechanism of OER, both OH
nique offers more broader range of testing conditions, including
and OOH binds via a single bond to the active metal center, the binding
discharge and charge current density, the total number of cycles, as well
energy of OH and OOH are linked with a constant difference (ΔGHOO*-
as the duration and/or cut-off voltage applicable to each cycle, each of
ΔGHO*) of 3.2 ± 0.2 eV. The value of ΔGHOO* can be directly obtained
these parameters will significantly influence the corresponding test
from the computed ΔGHO*. If that the gap between ΔGHO* and ΔGHOO* is
outcomes.
greater than the designated threshold of 2.46 eV (2 ×1.23 eV) predicted
for a catalyst, one may conclude a minimum theoretical overpotential of
1.2.3. Galvanostatic full-discharge
0.37 eV ([3.2–2.46 eV]/2. For the rate-determining step in the majority
The galvanostatic full-discharge testing procedure quantitatively
of OER catalysts, the difference between ΔGO* and ΔGHO*, i.e. (ΔGO*-
assesses the capacity of zinc-air batteries by applying a constant
ΔGHO*) may be employed as a universal descriptor to forecast their OER
discharge current until a defined cut-off voltage is attained. Given that
activity (Fig. 2(b))). According to the Sabatier principle, an ideal catalyst
the capacity of a zinc-air battery is governed by the zinc electrode, this
necessitates that the adsorption strength of the crucial intermediates be
capacity is frequently expressed in relation to the mass of the zinc
neither excessively robust nor overly weak. Consequently, the repre
electrode, this facilitates a comparative analysis against the theoretical
sentation of ηOER as a function of (ΔGO*-ΔGHO*) yields a universal
specific zinc capacity of 820 mAhg− 1. Furthermore, a specific energy
volcano-shaped correlation that remains steady across different catalytic
density normalized to the mass of zinc consumed (Whg− 1) can be
materials.
derived by multiplying the specific capacity with the average discharge
voltage sustained throughout the discharge interval. M + OH- → MOH + e− (7)
1.2.4. Electrochemical impedance spectroscopy MOH + OH → MO + H2O + e

− −
(8)
Electrochemical impedance spectroscopy (EIS) serves excellent MO + OH− → MOOH + e− (9)
analytical technique to elucidate individual resistances and capacitances
within a zinc–air battery, thereby facilitating a comprehensive under MOOH + OH− → M + O2 + H2O + e− (10)
standing of the major limiting factors. Typically, EIS in rechargeable
Other descriptor which plays a very important role in predicting the
zinc–air batteries is performed concerning the discharge and recharge
binding energy of the intermediate over metal is eg occupancy[30]. The
phenomena at a predetermined overpotential. The Nyquist plot derived
eg orbitals of the transition metal participate in σ bonding with surface
from the EIS is employed to analyze the resistances inherent in the
adsorbate. Previously explained that as the Sabatier principle of neither
system. Through the modeling of the Nyquist plot, one can find out
weak nor strong adsorption of intermediate is good for the OER, opti
various circuit components such as Rs, Rint, Rct, Qint, and Qdl. Rs and Rint
mum binding strength with oxygen containing intermediates can be
denote the resistance of the electrolyte and the interfacial resistance
achieved via regulating the eg occupancy. Higher the eg occupancy
between the electrode and electrolyte, respectively. Smaller values of Rs
weaker will be the bonding and lower the occupancy of eg orbital will
and Rint are indicative of reduced internal resistances associated with
increase the binding energy. Thus, the occupation of the eg orbitals of
the electrolyte and at the interfacial contacts, respectively, within the
transition metals, situated in an octahedral configuration can be
zinc–air battery. The quantification of interfacial resistance values holds
modulated by tuning their oxidation states and spin states. The
particular significance for solid-state electrolytes, owing to their rela
maximum electrocatalytic performance for the oxygen evolution reac
tively inferior wetting characteristics in comparison to traditional
tion (OER) is achieved when the occupancy of the eg orbitals approaches
aqueous electrolytes. Rct symbolizes the charge-transfer resistance of the
a value of 1.
air electrode during the electrochemical reaction, which is intrinsically
linked to the electrocatalytic efficiency of the air electrode. The constant
phase elements, Qint and Qdl, represent characteristic capacitances 2.2. Oxygen reduction reaction
arising from the interface between the electrode and the electrolyte. In
general, we can say that, a reduced charge-transfer resistance signifies Battery discharging efficiency, power density, and specific capacity
enhanced ORR catalytic activities (a similar trend applicable to OER of ZAB are greatly affected by the oxygen reduction reaction. Oxygen
activity during charging), culminating in an elevated discharge voltage. reduction reaction mechanism follows two distinct mechanisms, one is
3
Fig. 2. (a) Oxygen evolution reaction mechanism cycle (b) OER Volcano plots for metal oxides. Copyright with permission from AAAS (2017) [29] (c) 4e- and 2e-
oxygen reduction reaction mechanism (d) ORR volcano plot for different metals. Copyright with permission from AAAS (2017) [29].
2e- path and the other is 4e- path depending upon the orientation of the OER polarization and E1/2 is the half-wave potential for ORR potential
oxygen molecule as shown in Fig. 2(c). range. A truly efficient bifunctional catalyst should exhibit not only fast
OER/ORR kinetics but also must possess long-term durability, stability
M + O2 → MO2 (11) with low cost for commercialization. The combination of first-row
MO2 + H2O + e → MOOH + OH
− −
(12) transition metals with few second/third-row non-noble metals are the
perfect choice to make such efficient bifunctional electrocatalysts. In
MOOH + e− → M + HO−2 (2e− pathway) (13) this review article, depending upon the nature of the electrocatalysts, we
have divided the cathode materials into four different categories: (i)
MOOH + e− → MO + OH− (4e− pathway) (14)
metal oxides, (ii) Beyond metal oxides which include metal phosphides,
MO + H2O + e → MOH + OH (4e pathway)
− − −
(15) sulfides, and selenides (iii) Single-atom catalysts and nitrogen–carbon
materials with metals/alloys, and (iv) photocathode. In this review, we
MOH + e → M + OH (4e pathway)
− − −
(16) mainly focused on the fundamentals that affect the catalyst activity (eg
Oxygen molecule can be adsorbed in two different ways over metal occupancy, spin, and adsorption/desorption free energy) and we briefly
center, end to end adsorption follows 2e- path which gives the H2O2 is discussed the mechanism behind the improved activity of the catalyst.
the primary product while 4e- path is followed by bidentate adsorption
of oxygen molecule which gives OH- ion is the final product [18,31,32]. 2.3. Metal oxides
Oxygen reduction reaction follows multi-electron transfer via the for
mation of complicated oxygen-containing species O, OH, O-2 and HO-2. Transition metal oxide electrocatalysts are widely recognized for
The performance of ORR depends upon the adsorption and desorption of their ability in facilitating oxygen evolution reactions (OER) and oxygen
the reactants as well as the moderate binding affinity of oxygen to the reduction reactions (ORR), due to their partially filled d-orbitals that
catalyst. Insufficient binding energy does not facilitate the breaking of facilitate numerous possible oxidation states. Additionally, performance
the O-O bond, whereas excessively strong bonding hinders the desorp enhancement can also be achieved through doping or combining with
tion of the resultant product, thus blocking the active sites for subse other complementary materials like carbon-based materials. Through
quent adsorption of free oxygen molecules. In accordance with the doping, the eg occupancy was found to be modulated in few cases, e.g.
volcano plot that correlates the theoretical catalytic activity of ORR with Mathur et al. investigated the effect of Fe doping in MnO2 nanorods for
overpotential, as constructed by Nørskov et al., platinum (Pt) demon enhancing bi-functional oxygen electrocatalysis[34]. They have opti
strates the most superior catalytic performance for ORR[33]. The 20 wt mized the amount of Fe dopant for achieving high oxygen bifunction
% Pt/C composite is conventionally recognized as the standard bench ality. Inspired by their previous work, Mathur et al. applied the
mark catalyst for performance evaluation of synthesized ORR catalysts. co-doping of Ni and Fe in layered MnO2 for the bifunctional oxygen
Fig. 2(d) shows the ORR volcano plot for various metals. electrocatalysis [35]. The occupancy of the eg orbitals in
The criterion for the determination of an efficient bi-functional transition-metal cations situated at the octahedral (Oh) coordination
electrocatalyst involves the calculation of ΔE (ΔE = Ej10 – E1/2) which sites significantly influences the intrinsic properties of spinel oxides
can be measured by using linear polarization in OER and ORR potential towards ORR and OER, due to the pronounced overlap between eg or
range. Ej10 in the above equation represents potential at 10 mAcm− 2 for bitals and O2p orbitals of the oxygen-related adsorbates[36,37]. It is
4
proposed by Shao-Horn et al [38]. that the interaction of metal active formation of triplet O2 state, both adsorbed O* must have aligned spins.
site with the intermediate (M− OH− /M− O2− 2 ) directly affects the ORR This step is required to be mediated through a catalyst while Ni in its
and OER activities and this interaction can be altered by altering eg higher spin state can facilitate the spin alignment by hybridizing with
occupancy. Rao, Y et al. employed vanadium doping in Co3O4 spinel to the 2p orbitals of oxygen intermediates, ultimately reducing the over
alter its eg configuration[39]. Fig. 3(a) shows inverse susceptibility 1/χ potential for OER (Fig. 3(h)). Also, in-situ EPR data and DFT calculations
vs temperature plot (the straight solid lines are the fitting results based prove Ni in NiOOH/MnFeOOH has higher probability of being present in
on the Curie− Weiss law) of V− Co3O4 and Co3O4.Vanadium in its higher higher spin state due to charge redistribution at the hetero-interface, in
oxidation state +4 or +5 possess vacant d-orbital which is able to modify comparison to NiOOH. Also, the spin-polarized Ni, has unpaired elec
the electronic state of cobalt to e1g . Magnetic character measurements tron in t2g and eg orbitals which when hybridize with 2p of O* leads to
using Curie-Weiss law yields μeff=3.64 μB (Fig. 3(a)), which indicates formation of filled σ* antibonding orbitals. This lowers the energy bar
Co3+ being present in the catalyst with 50.5 % in H.S. and 49.5 % in L.S, rier for breakage of Ni-O bonds, facilitating O2 desorption. This work has
validating eg1 configuration. The catalyst shows exceptional bifunc shown the improvement in the OER activity by adjusting the spin states
tional activity with positive half wave potential (0.821 V) in ORR (Fig. 3 of electrocatalyst, without relying on external magnetic field.
(b)), low overpotential (350 mV) in OER and higher power density of Pure metal oxides (e.g. MnO2, CoO) only possess a single catalytic
120.3 mWcm− 2 (Fig. 3(c))and 40.6 mWcm− 2 when assembled in liquid site which either catalyze OER or ORR activity. On the other hand,
state and solid-state cable type battery respectively. This catalyst also catalyst with dual active sites can improve the activity significantly by
demonstrates higher rechargeability and stability (>4100 cycles, >57 providing active sites. Mechanically mixing of ORR-active component
days). The remarkable activity and stability is attributed to the optimum with an OER-active component is the most common strategy to achieve
binding of oxygen intermediates on the catalyst surface, facilitated by e1g bifunctional catalyst[44]. This method always results in a
configuration. Oh sites can affect the activity of these catalysts towards non-homogeneous distribution of the two constituent components, weak
OER and ORR[40]. The modification of eg state of Co3O4 was achieved interfacial architectures, and insufficient electronic modulation effects,
by doping it with nickel which can occupy both Td and Oh sites (Fig. 3 which unavoidably result in low catalytic activity and insufficient
(d)). The theoretical calculations via Density Functional Theory (DFT) durability over extended operational periods[45]. Therefore, strong
proved that Nioh-Co3O4 favors the ORR more, and hence they specif interfacial interactions are important to synthesize such efficient
ically synthesized Nioh-Co3O4 using Ni(OH)2 as a source apart from Ni bifunctional catalyst. Zhou, C et al. adopted a strategy that utilizes pure
(NO3)2. (Fig. 3(e)) Their observation indicated that introduction of Ni in oxide with dual active sites to overcome the drawbacks of single-site
Co3+changes the spin state of Co from L.S to H.S, resulting the eg oc catalysts and prevent carbon corrosion[46]. They synthesized atomi
cupancy less than 1, ideal for moderate absorption of ORR intermediates cally dispersed Mn atoms on RuO2 lattice, exhibiting high bifunctional
(Fig. 3(f)). It improves the pre-eminent ORR activity with high limiting activity with ΔE (0.64 V) and low half-wave potential (0.86 V) (Fig. 4c).
current density (5.87 mAcm− 2), higher E1/2 (0.84 V) and exhibits 86 % This exceptional activity is due to reduced valence state of Mn and Ru as
of current retention after 12 h of chronoamperometry. This catalyst proven by XPS (X-ray Photoelectron spectroscopy) and ELNES (energy
when used in an aqueous battery produces high peak power density of loss near-edge structure) spectra leading to unpaired electrons respon
78.4 mWcm− 2, specific density of 827 mAhg−Zn1 and remains stable for sible for the higher reactivity of the catalyst in comparison to high
42 h. This work utilizes computational as well as experimental tools to valence state of RuO2 or MnO2. The Mn-RuO2-based batteries exhibited
prove how eg occupancy in only octahedral site is important for ORRs higher open-circuit voltage (1.55 V), larger specific capacity of 812
and by modulating the eg state ORR as well as OER can be improved mAhgZn− 1 (Fig. 4(d)), and higher power density of 181 mWcm− 2.
respectively. The binding strength of the ORR/OER intermediates can be It has been elucidated previously that the dual active site catalyst
controlled through eg occupancy where reaction proceeds through the affords greater versatility by introducing an additional reactive center
four-step proton/electron-coupled reaction mechanism. The rate for bifunctional activity (Fig. 4(e)). The traditional *OOH mediated
limiting step will be controlled through the eg occupancy as for eg <1 the OER/ORR redox cycles are constrained by the binding energy "scaling"
Moct–O2− bond is so strong that the limiting step is OH− regeneration. of oxygen intermediates, particularly the two intermediary transitions of
On the contrary if eg>1, the limiting step is OO2− /OH− due to the *OH− → *O and *O → *OOH. A effective designing strategy is required
formation of stable stable Moct–OO2− [37]. for the intermediate scaling between *OH and *OOH, and facilitate the
The thermodynamics of adsorption of the intermediate on the cata OER/ORR cycle[47]. To break this linear scaling during OER, lattice
lysts’ surfaces have withdrawn enormous attention on the performance oxygen mechanism (LOM) has been introduced, compared with the
of oxygen electrocatalysis. Oxygen molecule being paramagnetic in “adsorbate evolution mechanism” (AEM)[48]. In LOM, lattice oxygen
nature, both oxygen evolution as well as oxygen reduction reaction serves as the redox center which activates and releases oxygen in
involve change in the diamagnetic hydroxide/water associated with the termediates from the lattice matrix, which enable the direct coupling of
spin-related electron transfer[41,42]. Both electron transfer and orbital O–O radicals[49]. The electrocatalysts tend to adhere to the principles of
interactions between the catalyst and the reactant/intermediate show LOM by augmenting the covalency of the metal− oxygen bond, which
spin-dependent character, making the reaction kinetics and thermody demonstrates a markedly improved OER activity; however, these elec
namics sensitive to the spin configurations[42]. Yang, L et al. have trocatalysts typically exhibit poor ORR activity and durability. For an
synthesized a spin-polarized modulated heterojunction Ni/MnFe2O4, example, Zhou, T et al. designed a dual-site electrocatalyst
which further undergoes reconstruction to form NiOOH/MnFeOOH, (MnxRu1− xO2) where bimetallic asymmetric M− O− Ru bridge structure
during OER[43]. The catalyst exhibits exceptionally high bifunctional promotes LOM by increasing the oxygen lability due to the enhanced
activity with a small gap (ΔE) of 0.68 V and higher open circuit voltage Ru− O covalency, where, Mn site in this dual-site catalyst also promotes
of 1.56 V, a higher specific capacity of 814 mAh g− 1, with higher ORR kinetics[50]. The optimized electrocatalyst Mn0.3Ru0.7O2 shows
durability for over 360 hours when assembled in a ZAB. The formation OER overpotential of 240 mV at 10 mA cm-2 (Ej10 at 1.47 V). Further
of stable triplet O2 required lower overpotential, in comparison to the more, the ORR performance of Mn0.3Ru0.7O2 electrocatalyst shows a
singlet O2. The unpaired electrons in eg and t2g can hybridize with O* to half-wave potential (E1/2) of 0.85 V, and the overall overpotential gap
form octahedral σ -antibonding with eg orbitals or π-bonding t2g orbitals (ΔE) for the electrocatalyst is 0.63 V which outperforms the mixture of
(Fig. 3(g)). Since it requires higher energy to form the antibonding standard benchmark catalysts (ΔE = 0.73) Pt/C+RuO2. With DFT cal
orbital, Ni3+ in a high spin state can decrease the bond energy barrier culations, it is concluded that Mn is the main active site for ORR and Ru
with O*, leading to a lower overpotential[43]. While oxygen in its is the main active site for OER (Fig. 4(h)). ZAB assembled with
ground triplet state has two unpaired electrons with parallel spins, hence Mn0.3Ru0.7O2 electrocatalyst gives a high specific capacity of 812 mg−zn1
according to the law of conservation of spin angular momentum, for the and it shows outstanding durability of 800 hours at 10 mAcm− 2 without
5
Fig. 3. (a) Inverse susceptibility 1/χ vs temperature plot (the straight solid lines are the fitting results based on the Curie− Weiss law) of V− Co3O4 and Co3O4 (b) the
corresponding E1/2, E10, and jk for V− Co3O4, Co3O4, and Pt/C− IrO2 at a rotating speed of 1600 rpm (c) Polarization curves and power density profiles. Copyright
with permission from ACS (2021) [39] (d) Schematic illustration of the preparation of electrocatalysts (e) Free energy diagram for the ORR on spinel Co3O4,
NiTd-Co3O4and NiOh-Co3O4 (f) Calculated effective magnetic moments (μeff) of the catalysts and eg occupancies of Co3+ in Co3O4 and NiOh-Co3O4, respectively
Copyright with permission from ACS (2023) [40] (g) OER process with and without the spin-aligned process (h) Illustration of the Ni3+ electron configurations with
low and high spin states. Copyright with permission from Wiley-VCH (2024) [43].
6
Fig. 4. (a-b) Images showing SEM and HAADF-STEM of the Mn-RuO2 (c) ΔE (ΔE = Ej10 – E1/2) comparison between Mn-RuO2 catalysts with standard catalysts and
with some other latest reported catalysts (d) Specific capacity of zinc-air battery with Mn-RuO2 and standard Pt/C+RuO2 catalyst with the inset showing the open
circuit plot. Copyright with permission from ACS (2022) [46]. (e-f) representation of OER/ORR bifunctional kinetics using single active site (M1) and dual active site
(M1 and M2) with the *OOH intermediate (g) In situ ATR-SEIRAS characterization using Mn0.3Ru0.7O2 catalyst during OER (h) Proposed LOM-mediated oxygen
evolution reaction/oxygen reduction reaction redox mechanism on the Mn0.3Ru0.7O2 catalyst based upon density functional theory analysis and experimental
characterizations. Copyright with permission from ACS (2024). [50] (i) Discharge i–v profile and its corresponding power density of Co@CoOx/NCNTs, Co/NCP, and
20 wt% Pt/C catalysts. Copyright with permission from RSC (2017) [53] (j) synthesis scheme of Co2Fe1@NC catalyst (k) Reported discharge polarization and power
density plot using Co2Fe1@NC catalyst. Copyright with permission from ACS (2020) [55].
any decay in the activity. to study the synergistic interplay between the oxide and hydroxides
Another work reported by Li, Y et al. shows an unprecedented micro/ [52]. They observed through controlled pyrolysis of CuCoOx precursor,
macrostructure engineered Ni-doped CoO nanosheets via. Cation ex Cu2O etches away due to the high diffusibility of Cu with simultaneous
change method, which exhibits improved O2 diffusibility with higher release of OH-, resulting in the formation of FeOOH nanoflakes over the
power density of 377 mWcm− 2 and durability over 400 hours[51]. core CuCoOx nanowires. The synergistic interaction between FeOOH
Moreover, four such button-like solid ZABs connected in series are suf and CuCoOx and improved mass/electron transfer due to highly porous
ficient to light up 17 LEDs and to charge a mobile phone. According to core structure formed after Cu2O etching, resulted in excellent bifunc
experimental and theoretical results, in addition to Ni doping, the syn tional activity with a small potential gap (ΔE) of 0.72 V. It also provides
ergistic effect of micro/nanoscale structure of Ni-doped CoO NSs with a ZAB with high power density of 158 mWcm− 2 and longer durability for
nanopores provide high diffusion of O2 molecules and abundant active over 20 hours. Porous carbon materials, due to their exceptional sta
sites thereby enhancing ORR activity. Similarly, to synthesize bifunc bility, elevated electronic conductivity, cost-effectiveness, and extensive
tional oxygen electrocatalysts other strategies like heterojunction for surface area, have been employed to fabricate composites with diverse
mation, and composite with carbon materials were also adopted. Kuang, electrocatalysts to enhance their electrocatalytic performance. Carbon
M et al. developed a composite CuCoOx/FeOOH via a three-step route, precursors originating from metal-organic frameworks present
7
advantages over conventional carbon precursors attributed to the co 840 mWhg− 1. Above all, it exhibits discharge stability at a high current
ordination of the metal center with electron-donating organic ligands. density of 500 mAcm− 2. Guo, X et al. have explored a non-traditional
Lin, C et al. utilize a new strategy to synthesize 1D MOF-driven carbon solid phase synthesis route for a multiphasic catalyst
materials, specifically Co@CoOx/NCNTs, to achieve an optimized Zn to Fe2O3/Fe5C2/Fe− N− C which can show synergistic behavior thereby
Co ratio, preventing Co-induced agglomeration of carbon framework enhancing electrocatalytic behavior [54]. By altering the ratios of the
[53]. Here, the author has explored three advantages of ZnO NWs, precursors melamine and ferrocene, different morphologies of nano
calling it “three birds with one stone” strategy i.e. ZnO nanowires acting tube, sheets, petals, spheres, and nanotube on microblocks are obtained.
as nucleation sites for ZIF-8 crystal growth, with its in-situ reduction and Despite having high bifunctional activity, catalysts exhibit less stability
evaporation leading to highly porous morphology contributing to high due to degradation at high charging voltage, resulting in power density
electrochemical surface area. Furthermore, release of excess oxygen much lower than the theoretical value. Tang, T et al. have explored a
during pyrolysis of ZnO NWs produces thin shells of CoOx on Co nano new strategy to achieve high-density metal supported over by a porous
particles, resulting in high bifunctional activity. Thus, the further carbon network and also encapsulated by graphitized carbon layers
assembled ZAB provides high open-circuit voltage (1.52 V), high peak (Fig. 4(j)) to provide long cyclability and results in a groundbreaking
power density of 353.3 mWcm− 2 (Fig. 4(i)) and high energy capacity of power density of 423.7 mW.cm− 2 (Fig. 4(k) and large specific capacity
Fig. 5. (a-b) high resolution XPS spectra of P 2p, and O 1 s for CoO/CoxP (c) ΔE (ΔE = Ej10 – E1/2) comparison of CoO/CoxP with various catalysts. Copyright with
permission from RSC (2020) [60] (d) TEM images showing Co/Co2P@NCNTs interface (e) Co K-edge XANES spectra of the Co/Co2P@NCNTs prior to and after the
ADT test (f) charge/discharge polarization performance of the Co/Co2P@NCNTs with its corresponding power density curves. Copyright with permission from ACS
(2021) [64] (g) schematic representation for the synthesis process of CoP@Co2P/NPC (h) discharge i-V plot along with power density curves. Copyright with
permission from RSC (2024) [65] (i) The free energies calculation of electrocatalytic intermediate steps along with the PDS energies (j) polarization plot of zinc-air
battery along with its corresponding power density (k) Schematic shows the Se-driven reconstruction mechanism. Copyright with permission from ACS (2023) [66].
8
of 812.5 mAh gZn− 1 with small ΔE of 0.80 V [55]. Experimental toward amorphous (oxy)hydroxide as the working phase with
observation reveals that controlled pyrolysis of the metastable oxide Se4+-involved configurations (Fig. 5(k)). Multiple operando and
results in formation of Co0.7Fe0.3 alloy having highly dense, small-size post-cycling characterizations with Se-atomic resolution validate its
nanostructure with 54 % metal loadings, with both Co and Fe present edge-sharing configurations and contribution on metal evolution. Deng,
in their metallic form which contributes to the large no. of active sites Y et. al. utilizes the complete reconstruction of (Fe, Ni)2Se which is
responsible for the exceptional electrochemical activity. caused by its instability in the alkaline medium during the charging and
discharging process, which leads to its enhanced bifunctional perfor
2.4. Beyond transition metal oxide mance with high power density of 126 mWcm− 2 which rises to
215mWcm− 2 after the third cycle, surpassing the 158 mWcm− 2 of NiFe
Recently there has been a surge in the designing and synthesis of (Fig. 5(j)). Theoretically, DFT helps in understanding the role of Se
transition metal sulfides, selenides, and phosphide-based electro which reduces the energy barrier (Fig. 5(i)) and increases the access to
catalysis for battery and fuel cell-based applications due to their higher active states by expanding the triphasic interface. The experimental
conductive nature than their respective oxides and better stability. results are validated by XANES spectra, as soon as the catalyst was
Various researchers have explored the synergistic effect between the dipped into the alkaline electrolyte reconstruction started, the Se K-edge
oxide and phosphide interface to study the electrocatalytic behavior spectra showed extra peaks for the presence of Se4+/6+ species which
[56–59]. Owing to advantageous characteristics including elevated enhances with cycles but in dry state peak for anionic state Se2- only was
electrical conductivity, as well as robust mechanical and thermal sta observed. Also, the stabilization of peak shapes after the third cycle
bility, transition metal sulfides have exhibited enhanced catalytic per indicates the cessation of the reconstruction. The complex Ni K-edge
formance in electrochemical reactions when compared to their metal spectra indicate the formation of an active oxyhydroxide state in the
oxide equivalents. Niu, Y et al. designed a highly porous “Trimurti” third cycle, providing additional evidence of activity through recon
catalyst where they specifically used cobalt phosphides due to their struction[66].
exceptional OER activity and cobalt oxides due to their better ORR ac The dual Co active sites at the interface of the heterojunction also
tivity, leading to synthesize an exceptional bifunctional activity. The in found to be effective in controlling the electrochemical activity. It had
situ synthesis of the catalyst provides a synergistic effect enhancing been reported that upon pyrolysis CoSe2 transformed from ortho
adsorption of ORR and OER intermediates. This led to enhanced inter rhombic to cubic phase leading to optimal eg filling and the subsequent
facial electron transfer which is also proven by presence of P-O peak in formation of in-situ heterojunction. This heterojunction promotes
XPS (as shown in Figs. 5(b). A small voltage gap (ΔE) of 0.74 between interfacial migration of electrons from CoSe2 to CoN, thereby balancing
OER and ORR in CoO/CoxP (Fig. 5(c)) indicating it has better charging the binding strength of oxo-intermediates. This modulation is respon
and discharging performance making it a good candidate for recharge sible for exceptional bifunctional activity with low ΔE (0.7 V) (Fig. 6
able ZABs. The battery procures high peak energy density (c)). The synthesized catalyst c-CoSe2-CoN/NC based ZAB shows better
(122.73 mW cm− 2) and remains stable for more than 400 cycles, 200 h performance with higher specific capacity of 802 mAh g−Zn1 and good
[60]. Through the application of sophisticated computational method cyclic durability for over 250 h. This is attributed to the encapsulation of
ologies and operando characterization techniques, a dynamic recon the heterojunction by hollow nanoporous cage of carbon, which im
struction has been elucidated, and three-dimensional metal (oxy) proves stability by preventing dissolution of active species, and, also
hydroxides have been identified as the pivotal role-player for reversible hollow structure allows better mass transport[67]. Cui, M et al. designed
O2 electrocatalysis[61–63]. The formation of 3d-metal (oxy)hydroxides an exceptionally stable heterojunction CoN/CoS2/NC encapsulated with
for O2 electrocatalysis also plays an important role for controlling graphydine, exhibiting exceptional bifunctionality. The outstanding
OER/ORR activity. Wu, M et al. explored self reconstruction of biphasic dual activity and stability was a confluence of many factors like -
Co/Co2P heterojunction (Fig. 5(d)) into a Co3+ Oh containing active incorporation of sulfur which promotes oxidation of Co 2+ species
species, which contributes to its high bifunctional activity. They boosting OER activity, and graphdiyne which through their π-in
observed that structural transformations like (i) greater quantity of teractions enhances formation of CoN and increases stability against
Graphitic-N active sites and (ii) formation of Co (oxy)hydroxide phase alkaline corrosion. Also, formation of heterojunction supports electron
from Co/Co2P produced at higher potential are responsible for enhanced transfer from CoN to CoS2, optimizing adsorption of oxo-intermediates
ORR and OER activity, respectively. The synthesized catalyst and reduced energy barrier (Fig. 6 (d))[68]. Niu, Z et. al. designed a
Co/Co2P@NCNT when assembled in solid state ZAB, exhibits enhanced catalyst Sb-SeNC, to improve the sluggish kinetics of oxygen reduc
cyclic durability for over 1080 hours[64]. Another work by Li, Z et. al. tion/evolution reactions at ultralow temperature and to achieve
shows the performance of the mixed phase CoP/Co2P heterostructured high-performance LT-ZAB. The prepared catalyst exhibits higher peak
nanoparticles confined N,P coped carbon through in-situ phosphidation power density of 275 mWcm− 2 and 54.1 mWcm− 2 at normal and low
(Fig. 5g). CoP@Co2P/NPC-0.5 catalyst has least overpotential, larger (-40◦ C) temperature respectively (Fig. 6 (e)). Experimental and theo
double layer capacitance, and less Tafel slope both in ORR (71.94 mV retical results validate the role of doping of an electron-rich heteroatom
dec− 1) and OER (94.40 mV dec− 1) suggesting it has good kinetics for Se on activity of Sb through long range effects, in fact SbN2C2 are found
both OER and ORR. Theoretical calculations also suggest that CoP@ to be the real active sites rather than SbN4, with SbN2C2 species having
Co2P/NPC has faster kinetics for both OER and ORR. Density of state strong absorption ability for oxo-intermediates. The introduction of Se
calculation suggested the energy of d orbitals of Co gets closer to fermi increases antibonding proportion of Sb-O bond, facilitating the opti
level due to the effective hybridization between Co, P, and P, C, which mized binding of intermediates. However, the effect of long-range
leads to more adsorption of oxygen intermediates and the lowest energy electron delocalization by Se was validated by constructing the vol
barrier for rate-determining steps of both OER (0.22 eV) and ORR cano type plot between Uonset and Se-N distance. This plot confirms that
(0.82 eV). also In terms of practical application, a ZAB is assembled and when Se-N distance is 7.4Å (long range) it exhibits greater absorption
found that it has procured high peak power density of 215.1 mWcm− 2 ability for OOH* and OH* compared to distance less than 7.4Å (Fig. 6
(Fig. 5(h)), specific capacity of 689 mAh g−Zn1, and have long life span of (f-g)). This results in change of RDS from initial *OH →H2O to *O→*OH,
580 h for charging and discharging [65]. Dynamic reconstruction of (Fe, thereby enhancing the ORR activity[69]. Many investigations have
Ni)-Se2 also had been reported to improve the catalytic activity of the demonstrated that integrating multiple elements in a single catalyst
FeNi alloy and hence improve and Zn− air battery behavior. This in material shows superior bifunctional activity[35]. Xu, Z et al. reported a
volves three steps (i) anionic oxidation from Se2− to Se4+, leaching as simple one-pot synthesis approach for Ag-based MENPs through incor
Se4+ from the selenide lattice and (ii) re-coordination of Se4+ onto the poration of non-metal, P to overcome the phase separation of Ag with
reconstructed surface and (iii) this drives the complete transformation other metals. The synthesized catalyst Ag-Ni-Fe-P MENP demonstrated
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Fig. 6. (a) Geometric phase analysis showing stress distribution in the ∈xx or ∈xy direction (b) Graph showing the relationship between Co k-edge absorption energy
(E0) and oxidation state (c) Polarization curves with power density plot for zinc air battery using c-CoSe2-CoN/NC and Pt/C (or RuO2) catalysts. Copyright with
permission from Wiley-VCH (2024) [67] (d) The Gibbs free adsorption energy plot of CoN, CoS2 and CoN/CoS2 for ORR and OER. Copyright with permission from
Wiley-VCH (2024) [68] (e) Polarization and power density profiles at a temperature of − 40◦ C using Sb–SeNC, Sb–NC, and Pt/C catalyst for solid-state zinc-air battery
(ZAB) (f) plot showing the onset potential of SbN2C2-1-Sen (when n = 1–5) (g) The structure representation and the separation between Se and N of SbN2C2-1-Sen (n
= 1–5). Copyright with permission from ACS (2023) [69] (h) ORR/OER polarization curves using Ag–Ni–Fe–P/C, IrO2, and Pt/C catalyst in O2-saturated 1 M KOH
solution (i) GCD profiles of rechargeable ZABs using Ag–Ni–Fe–P/C and Pt/C+IrO2 as catalyst. Copyright with permission from ACS (2021) [70] (j) Schematic
representation illustrating the procedure for the synthesis of metallic cobalt by the dealloying mechanism of bimetallic carbide Co3ZnC, achieved via the leaching of
zinc and carbon atoms (k) Plot showing the half wave potential and kinetic current at 0.87V. Reproduced from AAAS (2022) [71].
high bifunctional activity with a small potential gap ΔE of 0.63 V (Fig. 6 2.5. Single atom based
(h)), exceptional power density (234 mWcm− 2) and superior stability for
250 hours (Fig. 6 (i)). The enhanced activity was attributed to the A significant part of the heterogeneous catalysis is dominated by the
presence of multi-elements and their synergistic effects such as Ag acts transition metal-based catalysts, as represented by the fact that a ma
as main ORR active site with the activity promoted by abundance of jority of the state of art electrocatalysts are made of noble metals (such
Ag-Ni/FeP neighbor sites[70]. Emerging research identifies bulk defect as Pd, Pt, Ru, and Ir)[72,73] which also associated with high cost and
engineering as a top-notch strategy, as investigated by Meng, T et al. scarcity. This led to the emergence of the non-precious metal catalysts as
who examined the effect of FPD (Frank partial dislocations), a familiar a promising frontier in the field of electrocatalysis. In heterogeneous
bulk defect on the catalytic activity of cobalt. They observed that the catalysis, the reaction typically takes place at the surface or interface of
thermally dealloyed Co had higher number of vacancies in comparison the catalyst. In the case of bulk catalysts, only a minor proportion of the
to bulk Co (Fig. 6 (j)), which lead to formation of FPDs in Co and higher surface atoms participate in the catalytic processes which makes these
lattice strain responsible for optimal binding of oxo-intermediates. catalysts very wasteful thus, an effective strategy is required to enhance
Theoretical findings also indicate that FDP-Co possesses surface cata the utilization efficiency of catalysts by enhancing the fraction of surface
lytic sites with ΔEO* nearing the optimal value of ΔEO* = 0 eV, which is atoms engaged in the catalytic process and focusing on “Atomic Econ
responsible for its remarkable ORR activity characterized by an elevated omy”[74–76]. In a study by Zhang and colleagues in 2011, single-atom
half-wave potential of 0.90 V (Fig. 6(k)). When the synthesized catalyst catalysts (SACs) were described as catalysts that comprise atomically
is incorporated into a solid Zinc-Air Battery (ZAB), it demonstrates a isolated active sites[77]. In principle, SACs possess all metal atoms
substantial open circuit potential of 1.50 V and a high peak power exposed at the surface, thereby it is possible to achieve 100 % efficiency
density of 258 mWcm− 2[71]. in atomic utilization, which is particularly appealing for reducing the
10
costs associated with precious-metal-based catalytic materials[72]. In analysis suggests that FePc NTs-rGO have improved chemisorption of
metal-compound-based SACs, the active metal single atoms are uni OH- ions, resulting in formation of real active sites HO-Fe+3-N. The
formly dispersed across the surface of the metal compound. Because of formation of these Fe+3 sites were facilitated by tuning the ORR po
their higher surface energy, these single atoms catalysts suffer from the tential above the redox potential of Fe+2/+3, specifically in FePc NT only.
issues of instability. Hence, the strong metal-support interaction is These active sites have relatively less binding strength for
crucial for the stabilization of the individual metal atom which is typi oxo-intermediates in comparison to FePc (+2 O.S.) molecules, resulting
cally facilitated by metal bonding between the metal and non-metallic in excellent ORR activity with positive E1/2 of 0.88 V and also provides a
ligands (such as C, N, O, S, and P)[78,79]. A metal single-atom and ZAB with higher peak power density of 120.3 mWcm− 2[89]. The
non-metallic ligands composite forms a metal single-atom site. The inherent properties of noble metals make them an appealing option for
non-metallic ligands not only serve to stabilize the metal single atom but electrocatalytic applications. However, their high expense constrains
also modulate the electronic structure of the metal site, which subse their practical application. Metal-linked framework materials has
quently dictates the activity, selectivity, and stability of the catalysts proven to be the most atom-economical way to utilize high-cost metals
[80]. Fe-based single-atom catalysts are the most explored and common possessing exceptionally high electrocatalytic activity. Kumar, G et al.
within this category[81]. We shall now elaborate on the recent de utilizes single-step template-assisted synthesis of Pd-linked POP (Pd
velopments in single-atom catalysis. As ORR is the key process that POP) which is further pyrolyzed at 800 ◦ C to develop embedded Pd
governs the actual performance of the ZABs. ORR is the process occurs nanoclusters and Pd single atom doped nanocarbon (PDNC/Pd-NC800).
during the discharge of the ZAB. Therefore improving the ORR kinetics Here, the author has followed the strategy “Killing two birds with one
can allow us to achieve high specific capacity and power density. stone” i.e. cost-effectiveness by utilizing the least amount of electro
Various strategies has been employed to improve the ORR kinetics. Xu active noble metal-Pd and improved efficiency by developing a
et al. reported a template-assisted approach to synthesize atomically single-step method for C-C coupling and metal complexation, contrast
dispersed Fe atoms on N-doped carbon substrate by using a ing with traditional multistep complex synthesis. The constructed
water-soluble metal salt to enhance contact with the carbon substrate catalyst shows exceptionally high bifunctional activity with low E1/2 of
(Fig. 7 (a)). They observed that the catalyst Fe SAs/MC exhibits a high 0.85 V vs RHE, high limiting current density (jL) of 6.1 mAcm− 2 in ORR,
specific surface area (SSA) of 1130 m2g− 1, due to its mesoporous and a low overpotential (Ej10) 292 mV in OER by triggering the electron
honeycomb-like morphology (Fig. 7 (b)). The high SSA and enhanced transfer, adsorption-desorption of oxygen molecule and synergistic ef
mass transport are responsible for its excellent ORR activity, with a large fect of diffusion and spillover mechanism (Fig. 7 (i)). Catalyst gives
positive half-wave potential of 0.902 V (Fig. 7 (c)). Further, when the overall low ΔE of 0.67 V for bifunctional Kinetics (Fig. 7 (j). The results
catalyst is assembled as a cathode in ZAB, it provides high specific ca are validated by characteristic XRD peaks indicating presence of
pacity of 739 mAhg− 1 (Fig. 7 (d)), high energy density of 960 Whkg− 1 Pd-Nanoclusters and EXAFS peaks showing conversion of Pd-N6 (in Pd
and superior durability. It is also able to power up a LED of 3.7 V, when POP) into Pd-N4 center. The presence of Pd-Pd bond was found only in
three batteries are connected in series[82]. As we already know per PDNC/Pd-NC800 which is responsible for high conductivity due to elec
formance of heterogeneous catalysis is very much dependent upon the tronically well connected 2-D framework and enhanced surface migra
surface area. More the specific surface area more the platform available tion of reactants to active sites Pd-Nx by spillover effect of Pd
for reaction kinetics. Above discussed article is the perfect example of nanoclusters[84].
achieving high ORR performance by achieving high surface area using The majority of the synthesized single-atom catalysts were derived
mesoporous morphology. from the Fe-N-C framework, attributed to its reasonably favorable ac
Metal phthalocyanines (MPc), a well-known molecular catalyst, tivity and stability for the kinetics of the oxygen reduction reaction
possess a well-defined M-N4 coordination and customizable chemical (ORR). The Fe-N-C framework tends to facilitate the Fenton reaction.
environments and can provide the flexibility to attach various electron- However, its performance in the oxygen evolution reaction (OER) is
withdrawing and electron-donating substituents to the phthalocyanine considerably deficient due to the generation of the poorly conductive
moiety. This carbon substrates can facilitate a range of electrochemical intermediate FeOOH, which blocks the active iron sites and inhibits
phenomena efficiently and had been utilized to prepare various types of electron transfer[90]. Apart from density functional theory (DFT) in
single atom catalysts. Wu et al. have studied the role of nitro groups in vestigations, inspiration comes from biological systems to incorporate
manipulating energy levels of FePc structure and discovered the mech an alternative metal center within the Fe-N-C framework[91,92]. This
anism for directional interfacial electron transfer, which results in introduction of another atom can provide the additional active site the
outstanding ORR activity with high positive half-wave potential of OER reaction to happen and it can show synergistic effect with Fe-N-C
0.93 V (Fig. 7 (e)). The synthesized catalyst Fe-Pc-β-NO2-KJ provides a system which could significantly enhance the overall kinetics of both
ZAB with high peak power density of 366 mWcm− 2 (Fig. 7(f))and su processes. Sarkar, S et al. employed a ligand-assisted sequential strategy
perior durability for 160 hours. DFT data also suggests that α-NO2 to achieve isolated metal active sites, using a chelating ligand Ph-btpy to
configuration has mismatched energy levels after absorption of in synthesize FeCo-NC (Fig. 8 (a)). This approach effectively prevents
termediates due to steric effects, while β-NO2 remains co-planar with metal-metal agglomeration by anchoring the metal atoms at specific
carbon substrate maintaining matched energy levels for consistent sites. The constructed catalyst shows exceptional bifunctional activity
electron transfer[83] (Fig. 7 (g-h)). Therefore it can be concluded from with low ΔE of 0.75 V (Fig. 8 (b)) and high-power density of 198.4 mW.
the above example that just by changing the orientation or the sub cm− 2 and 158 mWcm− 2 when assembled in liquid and solid-state bat
stituents can alter the energy levels which can affect the kinetics of ORR teries respectively. The higher activity was ascribed to the weak ab
or any other catalytic process. Not only the orientation, position of the sorption of intermediates on the surface, which is the result of
substituent can also selectively affect the catalysis process. FePc dem downward shifting of d–band center of both the metals due to nitrogen
onstrates optimal efficacy in the electrocatalytic oxygen reduction re doping, validated by DFT calculations. The XANES spectra demonstrate
action (ORR) owing to its partially occupied d orbitals, which facilitate coexistence of isolated Fe-N4 and Co-N4 sites after pyrolysis of the
suitable O2 chemisorption [85,86]. Typically, FePc follows a octahedral precursor having free axial positions available for the reac
redox-mediated mechanism, which is inspired from natural enzymes like tant coordination (Fig. 8 (c-d)). Furthermore, the solid-state battery
cytochrome c (cyt c) and cytochrome c oxidase, both of them possess shows the performance of the device with red LED for 24 hours [93]. He,
similar iron coordination environments[87,88]. Wang et al. have stud Y et al. have studied the synergistic effect of two metal atoms with the
ied the role of morphology control on redox properties of molecule by coexistence of both octahedral and square planar active sites on the
evolution of FePc molecules into ordered nanotubes, which enhances bifunctional activity of the synthesized Fe, Co-NC catalyst from
stability and conductivity of the structure. The DFT and Pourbaix metal-organic framework precursor (MOF). The catalyst demonstrates
11
Fig. 7. (a) Schematic Representation of the methodologies for the Fabrication of Mesoporous Iron Single-Atom/Matrix Carbon Catalysts (A) and the Synthetic
Methodology of the Representative Iron Single-Atom/Matrix Carbon(950) Catalyst (B) (b) TEM Image of the mesoporous Fe SAs/MC(950) catalyst (c) half-wave
potentials and onset potentials of Fe SAs/MC(950) and Pt/C samples in the ORR potential range (d) Plot of Specific capacity comparison for the Zn–air batteries
using Fe SAs/MC(950) and Pt/C. Copyright with permission from ACS (2018) [82] (e) The evaluation of kinetic current density (Jk) at a voltage of 0.90 V and at
half-wave potential (E1/2) for the compounds FePc-β-NO2-KJ, FePc-KJ, and FePc-α-NO2-KJ (f) power density plot with polarization curve for FePc-β-NO2-KJ and
FePc-KJ catalysts (g) Schematic representation of the coplanar arrangement for FePc-β-NO2-KJ and (h) the noncoplanar arrangement for FePc-α-NO2-KJ for the
oxygen reduction reaction (ORR) process. Copyright with permission from ACS (2022) [83] (i) Schematic showing the bifunctional performance of the Oxygen
Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) on the PdNC/Pd-NC800 catalyst (j) ΔE value for oxygen reduction reaction (ORR) and oxygen
evolution reaction (OER) potential range using polarization diagrams for the PdNC/Pd-NC800 and commercially available catalysts (Pt/C+RuO2) Copyright with
permission from Wiley-VCH (2024) [84]. (k) Polarization plot and their areal power density graphs for the CNCo-600 and the commercially (Pt/C+Ir/C) catalyst.
Copyright with permission from ACS (2019) [112].
12
Fig. 8. (a) Two-step synthesis scheme for Fe,Co,N− C Electrocatalyst (b) Comparison of overall polarization plot in the ORR and OER potential window for the Fe,Co,
N− C and commercial (Pt/C+RuO2) catalysts (c-d) K edge of Fe and Co for the fitted structures of Fe,Co,btpy and Fe,Co,N− C catalysts. Copyright with permission
from ACS (2022) [93] (e) comparison of the ΔE value of Fe1Co3–NC-1100 with reference catalysts (f) Polarization curve and power density plot for Fe1Co3–NC-1100
catalyst and its comparison with standard 40% Pt/C+RuO2. Copyright with permission from ACS (2022) [94] (g) MO diagram of Co and Ni with oxygen showing the
mechanism of OER and ORR. Copyright with permission from ACS (2023) [95] (h) ΔE value of NSC, Fe/SA-NSC, Co/SA-NSC, Fe,Co/DSA-NSC and Pt/C&IrO2
catalysts (i) specific capacity plot at 10 mAcm-2 (j) Polarization curve with power density plot. Copyright with permission from ACS (2023) [97].
high bifunctional activity with lower potential gap of ΔE=0.702 V density of 194 mW cm− 2. Mechanism demonstrated that for OER Co and
(Fig. 8 (e)), exceptional power density of 372 mWcm− 2 (Fig. 8(f)) and for ORR Ni is the main active site as shown in Fig. 8(g). Square planar
maintains its stability for 190 h. The performance was ascribed to the Co+2 active site converted into Co+3 with five coordination sites and
formation of a unique geometry Fe, Co-OH-NC, which provides dual square planar Ni-N4 active site after adsorption of OOH* on metal
metal sites that are simultaneously active for both OER and ORR. The converted into a five-fold site. In the whole mechanism of ORR/OER on
results are validated by DFT calculations which show that the OH metal active sites pz-d2z molecular orbital interaction is involved[95].
adsorption energy to the FeCo− NC is negative indicating that FeCo Single metal catalyst embedded in N-C system as electrocatalyst has
− OH− NC is more stable than FeCo− NC. Further, the author explored been explored well. Some recent literature suggested poor performance
various doping ratios and annealing temperature, identifying of symmetrically linked metal-nitrogen M-N4 system, attributed to the
Fe1Co3-NC-1100 as the best catalyst, because it has the highest meso high electronegativity of nitrogen atoms, which influence the free
pore/micropore structure ratio, responsible for the enhanced mass adsorption energy for the intermediate products[85,96]. By incorpo
transport of oxygen and more accessible inner active sites[94]. rating other heteroatom with reduced electronegativity in M-N4 system
This Single atom-based catalysis not only confined to particular Fe- can be an effective solution for this problem. Yasin, G et al. reported a
based systems, other metals like Ni, Mn, and Co can be used to material with a precisely engineered microenvironment for Fe/Co atom
develop an efficient catalyst with a dual active site. Kumar, G et al. re with N/S surrounding environment over carbon substrate, which ex
ported a template-assisted synthesis approach of bifunctional electrode hibits exceptional bifunctional activity with ΔE value of 0.56 V Fig. 8
material CoNi-NC which is having dual active sites Ni-N4 and Co-N4 for (h). The catalyst Fe,Co/DSA-NSC when assembled in a solid ZAB dis
rechargeable zinc-air batteries. Their oxidation state and M-Nx unit played a high peak power density of 240 mWcm− 2 (Fig. 8 (j)) and a
present in the catalyst was confirmed using XANES and EXAFS respec larger specific capacity of 748 mA h g−Zn1 (Fig. 8 (i)). Further experi
tively. Low Tafel slope (50 mV dec− 1) of CoNi-NC catalyst suggested mental and theoretical results validate the formation of
faster electrochemical kinetics towards ORR. Catalyst achieved power asymmetrical-bridged active sites Fe(N2S)/Co(N2S), where
13
electron-deficient metals specifically act as active sites due to increased which incorporates M-N4 moieties and M4 nanoclusters coexisting on
interaction with nucleophilic oxo-intermediates. Additionally, the syn an N-doped Carbon support as shown in Fig. 9 (a). The catalyst exhibits
ergistic interaction of M-M bond alters the orbital position, to facilitate higher bifunctional activity with small E1/2 of 0.895 V (Fig. 9 (b) and
the kinetics/electron transfer during ORR/OER. Also, the Gibbs free provides a ZAB with high peak power density of 215.5 mWcm− 2 with
energy change of the reaction steps proves Co is the main active site for superior cyclability for 110 hours. The synergistic effect of SAC and
ORR and Fe for OER[97]. clusters, modifies the electronic structure of Fe/Ni active sites resulting
Another class of single-atom-based catalysts could be generated by in decrease of energy barrier for both ORR/OER, respectively. DFT
the integration of the nanoclusters or nanoparticles in conjunction with calculations further validate the specific roles of Fe4 and Ni4 clusters.
single-atom catalysts (SACs). The strategy can significantly enhance the Introduction of Fe4 nanoclusters over Fe-N4 active sites weakens the
catalytic activity and stability of the active metal sites for oxygen Fe-O binding, resulting in reduced energy barrier for the desorption of
bifunctional reactions by modulating their geometric and electronic OH* in ORR. Meanwhile, Ni4 nanoclusters facilitate the coupling of
configurations, along with enhancement in the interactions between the oxo-intermediates to Ni thereby enhancing the charge transfer in OER
active sites and their supporting materials, respectively[98–102]. Fan [103].
et al. have explored the synergistic effect of SACs and nanoclusters on To balance the energy dynamics associated with the adsorption-
activity of ORR/OER, by synthesizing the catalyst Ni, Fe-DSAs/NCs desorption of ORR intermediates, which is responsible for poor
Fig. 9. (a) Schematic showing the synthesis of Ni,Fe-DSAs/NCs (b) Bar graph showing current (Jk) at 0.85 V and half-wave potential (E1/2) for OER and ORR
respectively. Copyright with permission from ACS (2023) [103] (c) HR-TEM image FeY-NC catalyst (d) Discharge polarization plot with their corresponding power
density of FeY-NC, Fe-NC, and Pt-C catalysts (e) Free energy plot for ORR on YN4, FeN4, Fe4N, Fe4N-Y2O3 and FeN4-Y2O3 catalyst by using theoretical calculation.
Copyright with permission from Wiley-VCH (2024) [104] (f-g) OER and ORR performance of FeCo-SACs using 0.1M KOH solution. Copyright with permission from
ACS (2024) [105] (h-i) In-situ Raman analysis for OER and ORR processes respectively (j) d-orbital representation of Co in the CoN4 catalyst. (k) 3d orbital energy
levels of Cobalt (Co) in CoFeCu-TAC and Co-SAC. Copyright with permission from ACS (2024) [106].
14
electrocatalytic performance, Luo, R et al. synthesized a composite Pt/C catalysts. The role of Ni was validated through DFT calculations,
catalyst FeY-NC, where the inclusion of a rare earth metal Yttrium in suggesting shifting of the d-band center of Pt closer to the fermi levels.
duces the formation of a mixture of SACs, nanoclusters and hetero This shift facilitates the binding of oxo-intermediates but also raises the
structures and provides Fe4N0.94-Y2O3 and Fe-Nx-Y2O3 heterostructured energy barrier for the final desorption of *OH. These findings explain the
active sites. The synergistic effect of these dual active sites provides ideal superior ZAB performance while slightly lower ORR onset potential of
binding of oxo-intermediates, enabling the catalyst with higher E1/2 of PtNi/NC in comparison to commercially available Pt catalysts[111].
0.9 and 0.809 V in alkaline and acidic environments. The catalyst, when You, C et. al. synthesized N,Co doped Carbon material because N-C has
assembled as a cathode for ZAB, provides a higher peak power density of good activity for ORR like Pt but poor OER activity, hence to enhance
233 mWcm− 2 (Fig. 9 (d)) and exceptional specific capacity of 772 mAh OER activity cobalt is used. They synthesized CoNC nanospheres with
g−Zn1[104]. Uncertainty in the coordination environment of dual active little modification by altering annealing conditions. They observed as
sites within single-atom catalysts (SAC) may affect the adsorption and temperature increases N content decreases and sp2 carbon increases
desorption free energy of the intermediates[107,108]. Such modifica which leads to an increase in conductivity. To understand the role of
tions can significantly enhance both electron transfer and catalytic ef Cobalt, acid leaching of cobalt was performed and discovered through
ficiency. Wu et al. adopted a two-step non-traditional route to synthesize EJ10 and E1/2 decays that Co is the active site for both OER and ORR. In
FeCo-SAC with abundant and asymmetrically coordinated, N3-Fe-Co-N4 real-life application in ZAB, this catalyst shows an unprecedented power
active sites, demonstrating excellent bifunctional activity with smaller density of 479.1 mW cm− 2 (Fig. 7 (k)), the highest ever recorded[112].
ΔE of 0.616 V. The higher activity was ascribed to the upshifting of The following table have listed the different cathode materials for Zn air
d-band center towards fermi level on introduction of Co which results battery (Table 1).
due the coupling of 3d orbitals of Fe and Co, increasing electron transfer.
This upshift weakened the desorption energy of *O, favoring the 2.7. Photo rechargeable zinc air battery
adsorption and formation of *OH, further enhancing ORR catalytic ki
netics and activity as shown in figure Fig. 9(e). The synthesized catalyst, Recently there is surge in research for harvesting solar energy as its
when assembled as ZAB, exhibits peak power density of irradiation on earth is very high (2300 TW) as compared to the global
203.36 mW cm− 2 and superior durability for over 550 hours. Its energy consumption (16 TW)[133,134]. Photocathode is a potential
long-term stability was further tested by fabricating flexible wearable candidate for harnessing solar energy in zinc-air battery. Electron-hole
electronic devices like watches and biomedical electronics[105]. pair generated at cathode during illumination can take part in
Inspired by dual metal active sites in a single catalyst to alter the elec reduction-oxidation reaction that can improve the kinetics for ORR/OER
tron state of electrocatalytically active sites in SAC Zhong, J et al. processes, therefore, improving the battery performance. Yuliang Li
explored a triatomic catalyst having Cu, Fe, Co atoms dispersed on synthesized multifunctional electrode fabricated with nitrogen doped
N-doped graphitic carbon. The constructed catalyst shows high bifunc graphdiyne (N-GDY), which has the potential to act as photoelectrode as
tional activity with a low E1/2 (0.891 V) in ORR Fig. 9(f), a reduced well as oxygen bifunctional electrocatalyst. Its band gap is found to be
overpotential (310 mV) in OER Fig. 9(g) and an overall low ΔE 2.12 eV calculated by Tauc Plot as shown in (Figs. 10a).
(0.651 V), surpassing all other catalysts. Additionally, it exhibits high Charge-discharge cycles at 1 mAcm− 2 are shown in Fig. 10(b) for both
power densities of 208 and 184 mW cm− 2, when assembled in aqueous dark and illumination condition. As can be seen from Fig. 10(b) that
and quasi-solid-state ZAB respectively. XNAF and EXAFS analysis in voltage requirement to charge the device is very less in illumination as
dicates presence of M-N4 active sites with no M-M bond present for all compared to the dark conditions. Charging process carried out on
triatoms. In-situ Raman confirms Co being the main active site for ORR
and Co, Fe for OER, which were further validated by DFT calculations Table 1
(Fig. 9 (h-i)). Additionally, it confirms Co as the main active site with its Some other recent reports on cathode materials and their properties associated
d–band center lowered due to the introduction of Fe and Cu that weaken with ZAB.
binding to oxygen intermediate hence decreasing the energy barrier and
Sr. Cathode ΔE No of Power density Reference
resulting in energetically smoother OER and ORR kinetics Fig. 9(k) No. Material Cycles/
[106]. Hours
1 MS-CoSA-N- 0.76 350 160 mW⋅cm–2 [113]

2.6. Carbon-nitrogen materials with metals/alloys C− 800◦ C
2
2 CoSe2@NC 0.74 500 137.1 mW cm− [114]
Carbon-based materials are widely used substrates because they are 3 NiFeP/Pi 0.62 V 300 395 mW cm–2 [115]
4 Fe–N4 and 0.72 V 1035 185 mW cm–2 [116]
highly conductive, porous and their properties can be easily tuned by NiFe2O4
doping with various kind of heteroatoms. Generally, their synthesis re 5 Co/CoFe@NC 0.70 V 550 146.6 mW cm–2 [117]
quires high temperature, with no control over size-distribution and 6. FeCoNiMnV - 1698 185.12 mW cm− 2
[118]
thickness of carbon shells. To solve this problem, Waterhouse et al. HEA/N-CNTs
7. FeNi@NCNT-CP 0.73 V 10,000 200 mW cm− 2 [119]
introduced a synthesis strategy that allows control over size distribution
8. Co3O4/Co@NC 0.63 V 3600 123.46 mW cm− 2 [120]
and thickness of shell, while operating at low temperature. They syn 9. FeS2–CoS2/NCF 0.76 V 1244 257 mW cm− 2 [121]
thesized CoNi alloy nanoparticles encapsulated by thin N-doped gra 10. FeCoNi@HNC 0.82 V 200 109 mW cm− 2 [122]
phene shells via pyrolysis at 600 ◦ C, which exhibits a positive E1/ 11. Ni–Co–S/NSC 0.73 V 180 137 mW cm–2 [123]
12. CoNiP/PNC 0.86 V 57 h 171.0 mW cm− 2 [124]
2=0.83 V in ORR and a small overpotential of 366 mV in OER, enabling
13. Fe/Fe3C@N- 0.71 V 300 h 206 mW cm− 2 [125]
a ZAB with high peak power density of 155.5 mWcm− 2. DFT calculation doped CNT
validates the superior activity due to transfer of electrons from CoNi 14. Zn–Ni3FeN/NG 0.74 V 180 h 158 mW cm− 2 [126]
alloy to N-doped graphene shells[109]. Dispersion of various transition 15. ZnCo-ZIF@GO 0.90 V 50 39.5 mW cm− 2 [127]
metals or their alloys onto the carbon substrate can introduce additional 16. RuOx- 0.71 V 250 h 150 mW cm− 2 [128]
nc@Co3O4–250
active sites, which significantly improve the performance of the oxygen
17. Fe2Ni@NC 0.742 V 500 126 mW cm− 2 [129]
evolution reaction (OER) and the oxygen reduction reaction (ORR) 18. 3DOM- 0.76 V 236 h 253 mW cm− 2 [130]
[110]. Similarly, PtNi nanoalloy supported over N-doped Carbon sub MgxCo3− xO4
strate exhibits improved ORR activity and superior ZAB performance 19. Fe0.5Co0.5Ox/ 0.78 V 120 h 86 mW cm− 2
[131]
with high power density of 168 mW cm− 2, and an increased specific NrGO
2
20. CaMnO3/S 0.94 V 120 152 mW cm− [132]
capacity of 678 mAh g−Zn1, surpassing the performance of commercial
15
Fig. 10. (a) Band structure characterization (b) Cycling charge-discharge performance at 1 mA cm− 2 (Inset: enlarged view of 120 to 130 cycles). (c) The mechanism
of SZAB. (I) Structure of N-GDY-based SZAB. (II) Process at cathode and (III) Process at anode of SZAB.Reproduced from AAAS (2024) [135] (d) Energy levels
diagram of pTTh and molecular orbitals of O2 (e) ORR LSV plot (f) Charge/discharge plot of the Zn–air battery with pTTh as the cathode under illumination and with
CP and Pt/C without illumination at 0.1 mAcm-2. Copyright with permission from Wiley-VCH (2019) [136] (g) Charge/discharge profile of the Zn–air battery
showing voltage gap (h) the specific capacity at 20 mA cm-2 with and without illumination. Copyright with permission from RSC (2019) [137] (i) Power density plot
of cobalt-doped δ-MnO2 in dark and light conditions. Copyright with permission from Elsevier (2021) [138].
illumination, photon energy gets used up by N-GDY to generate performance in light conditions shows an onset potential of 1.52 V vs
electron-hole pair. Photo-generated vacancies in the valence band RHE which is 0.07 V lower than the performance in dark conditions.
exhibit a strong tendency for oxidation, facilitating proton removal, Under light illumination, the charge-discharge voltage gap is 0.82 V
migration towards the surface of N-GDY, and thereby promoting the which is much lower than voltage gap in dark conditions (1.01 V)
catalytic performance of N-GDY in the oxidation of OH- to yield O2. On (Fig. 10g). Enhancement in discharge capacity from 711 mAh g−Zn1 to 769
the other hand, the photo-generated electrons in the conduction band mAh g−Zn1 is noted when we change the condition for discharge from dark
travels through the external circuit towards the Zn electrode, thereby to light (Fig. 10h)[137]. A. Mathur et al. utilized cobalt intercalated
assisting in the reduction of Zn(OH)4 2− to Zn as can be seen from the sheets of Manganese oxide for photoenhanced rechargeable zinc-air
mechanism in Fig. 10(c)[135]. In another work, Jun Chen et al. had battery. 5CMN upon illumination gives enhanced power density
synthesized polymer semiconductor polytrithiophene (pTTh) as cathode 29.60 mW cm− 2 which is four times higher value than in dark condi
material for enhancing ORR kinetics by harnessing solar light for tions (7.66 mW cm− 2) (Fig. 10i)[138].
rechargeable zinc-air battery. From ultraviolet-visible spectrum, ab
sorption edge neat 630 nm is observed, which corresponds to a band gap 3. Electrolyte
of 1.97 V. Under illumination, strong EPR signal indicates the formation
of pTTh radicals which implies that electrons go from conduction bad of An electrolyte is one of the most important component in battery
pTTh to π2p* orbitals of O2 as shown in Fig. 10(d). ORR performance of technology which communicates between cathode and anode, analo
pTTh are shown in Fig. 10(e) which suggest that under illumination gous to the blood as the transporter in human body. At present, KOH is
onset potential of pTTh is 1.40 V which much better than 0.96 V and the most prominent electrolyte that is reported for rechargeable ZABs
0.64 for pTTh under dark and Pt/C. Upon irradiation, generated due to its high ionic conductivity (550 mS cm− 1 for a 35 wt% KOH
photoelectron in the conduction band of pTTh are accepted by O2 solvent at 25◦ C), minimal viscosity (2.2339 mPa s), and large oxygen
molecules which generates HO-2, which then disproportioned to OH-. diffusion coefficient[139]. Due to the open cell assembly of ZAB, there is
Discharge/charge curves at 0.1 mAcm− 2 are shown in Fig. 10(f). The always a chance of mechanical deformation of the battery which leads to
discharge plateau of pTTh-L is measured at 1.78 V, which is higher than the leakage of electrolyte. Recently there has been a sudden rise in the
the respective value of Pt/C (1.38 V) and CP (1.29 V) by 400 and demand for flexible electronics in health care and sports industries
490 mV, respectively[136]. Metal oxides with suitable band gap can which requires flexible energy storage systems that can withstand
also harness solar energy by generating electron-hole pair for zinc-air deformation without any loss of electrolyte. For practical applications, a
battery. Montree Sawangphruk et al. synthesized Co3O4 spinel with a novel electrolyte should have properties like high ionic conductivity,
direct and indirect band gap of 2.20 and 1.35 respectively. OER resistance to deformation, and high-water retention property. Solid
16
polymer electrolyte was a great choice to replace liquid electrolyte as it long cycle life of 54 h at 3 mAcm− 2 (Fig. 12 (d)) [143]. Another group
possesses high elastic modulus and thus resistant to deformation. But reports a bioinspired quasi-solid electrolyte (HAcc@HPPAN COONa/
solid polymer electrolyte comes with the big disadvantage of very poor PANa) to enhance ionic conductivity and water retention properties.
ionic conductivity which inhibits its use as electrolyte. To solve these QSEs exhibit a semi-interpenetrating network architecture, which is
problems, quasi solid-state electrolyte /gel polymer electrolyte (which is constructed through in-situ formation of a PANa-based hydrophilic
an intermediate state between solid and liquid electrolyte) is a potential hydrogel network, integrated with quaternary ammonium (HAcc)-
candidate as it possesses decent ionic conductivity in the order of grafted hollow porous polyacrylonitrile nanofibers (HAcc@HPPAN-
10− 4-10− 3 Scm− 1 at room temperature, high flexibility, and good water COONa) (Fig. 12 (e)). PANs network delivers an attractive gel
uptake capacity. The “Grotthuss” mechanism” is the primary mechanism electrolyte matrix with good water uptake (Fig. 12 (f)), while the
for the transport of OH− across the alkaline membrane and the func HAcc@HPPAN-COONa nanofibers with interconnected microchannels
tional group of polymer chain provides ion highway for their movement and HAcc moieties work as extra water reservoirs and ionic conduction
which is shown in Fig. 11. Mainly OH- ion in the electrolyte (exists in accelerators for OH-. HAcc@HPPAN-COONa/PANa shows a strain of
OH-(H2O)4-) which is considered as inactive form and by breaking an 500 % under mechanical deformation and toughness of 20082.3 kJm− 3
hydrogen bond in the first solvation shell, it forms active OH-(H2O)3- suggesting the superiority over HAcc@HPPAN-COONa and PANa.
solvation state. The hydrogen of OH- ion of OH-(H2O)3- state forms an Stiffness and toughness are provided by HAcc@HPPAN-COONa nano
H-bond with another H2O molecule, as a consequence of this, the initial fibers which effectively dissipate energy via the covalent
OH– anion is now transformed to a tetrahedrally solvated H2O molecule, bond-sacrificial mechanism[144]. Flexibility and stretchability are
which is a water molecule with an ideal bulk solvation pattern[140, provided PANs soft network. Meanwhile, the presence of HAcc acts as a
141]. This quasi-solid-state electrolyte can also act as a separator be dynamic binder via hydrogen bonding and electrostatic interactions
tween two electrodes. Polymers like PVA, PAA, PEO, cellulose fibers, with HPPAN-COONa nanofibers and PANs, providing additional flexible
PAN, and gelatin, etc. are extensively used to make a noble and elastic network. Abundant hydrophilic functional groups in fully
quasi-solid-state-electrolyte. These polymers independently do not show crosslinked porous network of HAcc@HPPAN-COONa/PANa electrolyte
all the properties which is required to make a good-quality electrolyte allow high water adsorption and storage which enhance the transport of
therefore, modifications of these polymers by using different strategies OH− 1 in the matrix, showing electrolyte and water uptake of 16.4 and
are crucial requirements to enhance their properties. 158.2 g g− 1 respectively Fig. 12(g). HAcc@HPPAN COONa/PANa elec
Among many strategies, the crosslinking strategy is one of the oldest trolyte shows ionic conductivity of 113.7 mS cm− 1 which is higher than
techniques to enhance the properties of polymers which uses certain that of HPPAN-COONa/PANa (108.6 mScm− 1) and PANa
crosslinkers to crosslink two different polymers. Li, W et al. synthesized (101.5mScm− 1) which is 4.4 times higher than that of the pristine PVA
PVAA-cellulose flexible solid-state electrolyte by simple physical cross- electrolyte (25.8 mS cm− 1). The FZABs with the
linking process between polymer chains of PVA and PAA and cellulose HAcc@HPPAN-COONa/PANa QSEs deliver excellent electrochemical
fibers (Fig. 12 (a)). The existence of large quantity of hydrogen bonds performances with a long galvanostatic charge-discharge lifespan of
between the polymer chains of polyvinyl alcohol (PVA), polyacrylic acid 100 h, high power density of 126 mWcm − 2 and good flexibility to
(PAA), cellulose fibers and water molecules, solid-state electrolyte endure routine deformations[145]. Electrode-electrolyte interface plays
shows elevated ionic conductivity of 123 mScm− 1, enhanced water an important role in battery performance as non-uniform interface in
retention, and excellent mechanical properties. From FT-IR, it is found creases the chances of dendrite growth and ZnO formation due to
that there is notable strengthening and broadening of O− H vibration non-uniform electric field. Cai, S et al. synthesized highly inter
peaks associated with PVAA and PVAA-Cellulose. This strengthening of connected porous poly(vinyl alcohol)/ poly(ethylene glycol) (PVA/PEG)
O− H vibration peaks suggested the existence of abundant hydrogen hydrogel electrolyte utilizing an ice-crystal template which uniformly
bonds in PVAA and PVAA-Cellulose (Fig. 12 (b)). Extension of O-H vi distributes electrolyte at the interface (Fig. 13 (a)). The ionic conduc
bration peak towards low frequency implies the presence of semi-free tivity of PVA/PEG composite membrane is 42.5 mScm− 1 which is higher
water molecule in PVAA-Cellulose that ultimately helps to improve than PVA gel (27.3 mScm− 1). Because of its highly interconnected
water retention[142]. The unique hydrogen bond network formed be porous architecture and high ionic conductivity of PVA/PEG, the elec
tween the functional groups of PVA, PAA, and cellulose in trolyte is uniformly dispersed in the gel and the movement of water
PVAA-Cellulose SSE can provide numerous ion-transfer paths, thereby molecules is constrained. As a consequence of this, the absence of
improving the ionic conductivity of OH− as shown in Fig. 12 (c). dendrite formation and hydrogen evolution at the interface of the
Assembled solid-state ZAB with PVAA-Cellulose SSE gives a maximum PVA/PEG composite gel improved the reversibility of the
power density of 74 mWcm− 2 specific capacity of 724 mAhg−Zn1, and a plating-stripping process due to its highly interconnected porous
Fig. 11. OH– migration occurs through a Grotthuss Mechanism in a gel polymer electrolyte. Pathway of OH- ion migration is shown by the directional arrow. During
this OH– migration, existed H-bond (shown in blue) is broken and a new H-bond (shown in pink) is formed.
17
Fig. 12. (a) Procedure for the synthesis of PVAA-Cellulose SSEs (b) FT-IR spectra of PVA, PVAA, and PVAA-Cellulose SSEs (c) Ionic conductivity as a function of time
plot after storage for 72 h (d) GCD cycling profile of the button-type solid-state ZABs with PVA, PVAA, and PVAA-Cellulose SSEs at 3 mA cm− 2. Copyright with
permission from ACS (2023) [143] (e) Schematic representation of non-covalent interactions within HAcc@ HPPAN-COONa/PANa (f) Real-time water and elec
trolyte absorption curves (g) water and electrolyte uptake comparison (h) Schematic illustration of ion-transport mechanism in HAcc@HPPAN-COONa/PANa QSEs.
Copyright with permission from ACS (2023) [145].
structure which allows the uniform distribution of electrolyte in gel method. the biomass. SSEs show mechanical robustness, high
(Fig. 13 (b)). PVA/PEG-based ZABs displayed a long charge-discharge water-retention capacity of 15 g g− 1, and high ion conductivity of 175
cycle life of 46 h, which is 10 times superior than pure PVA gels. The mS cm− 1 (Fig. 13 (e))simultaneously. The high ion conductivity is
PVA/PEG-based ZABs also shows a high power density of 109 mW cm− 3 mainly due to the plenty of penetrating ion and water channels for fast
(Fig. 13 (c))[146]. Dou, H et al. utilized robust and natural cellulose OH− conduction. Additionally, molecular dynamics simulation used to
nanofibers to synthesize environmental-friendly and intrinsic OH− visualize layered nanostructure of biomass SSEs, which shows the
conductive biomass SSEs (ICNF/WCNF) with mesh structure, in which alternating arrangement of hydrophilic and hydrophobic segments
the OH− conductive cellulose nanofibers (ICNF) and water-retentive under nanoconfined environment contributes to form successive ion and
cellulose nanofibers (WCNF) are knitted together to form the pene water channels, confirming the fast OH− conduction. Biomass-derived
trating ion and water channels by using energy-efficient tape-casting SSEs in ZAB exhibit excellent electrochemical performance with a
18
Fig. 13. (a) Schematic illumination of fabricating porous PVA/PEG gel (b) Schematic illustration of zinc plating/stripping in PVA and PVA/PEG gel (c) Power density
curves. Copyright with permission from ACS (2023) [146] (d) Mechanism of water retention of KOH-PAA hydrogel with NaCl doping [150]. Copyright with
permission from Wiley-VCH (2023) (e) Ion conductivity of biomass SSEs at different water uptakes. Copyright with permission from Wiley-VCH (2024) [147] (f) Bar
graph showing ionic conductivity calculated from bulk resistance (g) Post battery SEM image of 0.32 wt% o-g-C3N4/PVA membrane (h) Post battery SEM image of
PVA membrane. Copyright with permission from RSC (2024) [152].
peak power density of 126 mWcm− 2 and an ultra-long cycling life of small pores act to mitigate the loss of water in the gel matrix. The
over 31 h[147]. calculated ionic conductivity of the KOH-PAA hydrogel with 0.5 M NaCl
The addition of inorganic substances like KI, LiCl, NaCl etc[148]. are and 1 M NaCl remained the same at around 170 mS cm− 1 at room
used to enhance ionic conductivity and water retention abilities of gel temperature. Solid-state ZAB assembled with 1 M NaCl-KOH-PAA gel
polymer electrolytes. Keliang Wang et al. synthesized KOH-PAA gives the longer charge-discharge cycle life of 31 h which is superior to
hydrogel doped with a high concentration of NaCl to enhance the KOH-PAA hydrogel and 0.5 M NaCl-KOH-PAA hydrogel[150]. Inorganic
overall performance of the hydrogen in ZABs. The water retention fillers in the polymer matrix can enhance its properties like ionic con
properties of ordinary KOH-PAA hydrogel and KOH-PAA hydrogels ductivity and water retention ability by increasing the amorphous na
infused with varying concentrations of NaCl were studied. Results show ture in the polymer due to the disturbance in their long-range order in
that the weight loss of hydrogel electrolyte decreased after adding NaCl polymer chains. Wenbin Hu et al. synthesized Porous PVA with doped
to it which suggests superior water retention ability with the NaCl SiO2 to enhance the ZAB performance by increasing ionic conductivity
doping. This can be explained as during crosslinking of acrylate there is and water adsorption behavior. SiO2 has plenty of hydrophilicity due to
large amount of free water available that leads to the formation of large its oxygen therefore that can act as a push for water adsorption. They
polymeric mesh structure of ordinary KOH-PAA. Due to the addition of observed the increase in amorphous nature with the addition of SiO2
NaCl, acrylate crosslinking is affected by Na+ and Cl− . These ions concentration which increases the ionic transport because of more
transforms the free water into bound water, which diminish the mobility amorphousness, more hydrophilic domain near the hydroxide ion. With
of free water and it results more compact and dense polymer mesh ar the addition of SiO2 fillers, the electrolyte uptake reaches its highest
chitecture (Fig 13 (d)). Additionally, after doping of NaCl, the polymer value of 233 % with 5 wt% SiO2 and ionic conductivity for 5 wt% SiO2 is
network structure is altered by the salting effect and ions form hydrogen 57.3 mScm–1 which is also highest as compared with the other con
bonds between the polymer chains, thereby resulting in the spontaneous centrations of SiO2 in PVA. ZAB fabricated using PVA-5wt% SiO2 GPE
collapse of polymer chains and formation of the small pores[149]. These shows long charge-discharge cycling life of 48 hours and a peak power
19
density of 62.6 mWcm–3 which are superior to PVA[151]. and (3) electrocrystallization (Zn nucleation and growth)[162]. As
Singh, A et al. also adopted the addition of fillers method to enhance shown in Figs. 14–16(b), firstly, during the charging process, Zn2+ ions
the ionic conductivity and mechanical strength of PVA membrane[152]. near the electrode surface reduced to form Zn nuclei which produces a
They have used o-g-C3N4 as fillers to disturb the crystallinity to increase concentration gradient of Zn2+ ion between electrode surface and bulk
the ionic conductivity. The increase in the amount of o-g-C3N4 improves electrolyte[163,164]. This change in concentration gradient will induce
the ionic conductivity until the amount of o-g-C3N4 reached 0.32 wt% a deviation of electrode potential from equilibrium potential, thereby
o-g-C3N4 (27mScm− 1) (Fig 13 (f))after that conductivity decreases. The facilitating the accumulation of Zn atoms on the deposited nuclei[165,
decrease in conductivity after the addition of excess o-g-C3N4 can be due 166]. It should be acknowledged that the electrode surfaces are not al
to aggregation, which can block the path of ions, resulting in a decrease ways smooth and flat. Consequently, Zn nuclei tend to be formed at
in ionic conductivity. The calculated Young’s modulus 0.32 wt% regions high curvature tip such as dislocations, boundaries, and impu
o-g-C3N4/PVA composite at 10 % strain is 88.95 MPa which is superior rities, resulting in inhomogeneous Zn deposition, a phenomenon known
to the PVA (107.63 MPa). The improvement in mechanical performance as the “tip effect”)[167–171]. This cumulative effect of concentration
can be possibly explained by the increased hydrogen bonding between gradient and tip effect will influence the formation of dendrites. Zinc
the o-g-C3N4 chains and PVA. The galvanostatic charge-discharge plate and zinc powder are the most commonly used standard anode
behavior of o-g-C3N4/PVA membrane in ZAB was stable for up to 40 h material for Zinc-based batteries. Zinc powder is a better choice than
for 240 cycles which is much higher than PVA membrane (13 h). Zinc foil as it allows the full utilization of zinc, furthermore, particle size
Post-battery SEM images suggest less formation of dendrites in distribution and surface area can be tunable in case of zinc powder. Zinc
o-g-C3N4/PVA membrane as compared to the normal PVA membrane powder has the potential to be compatible in flexible battery technology.
which implies the better mechanical behavior of o-g-C3N4/PVA mem Among various strategies, anti-corrosive or protective coating of
brane can suppress the dendrite growth thereby enhancing cyclic per polyethylene glycol(PEG) surfactant over zinc powder (Zn-P/PEG) is
formance (Fig 13 (g-h)) (Table 2). employed to suppress the side reaction and dendritic growth where
surfactant played a dual role for the suppressing corrosion of Zinc anode
4. Anode [172]. It helps in the enlargement of Zn (002) crystal plane during zinc
decomposition process along with the protection of Zn anode from water
The anode is the actual powerhouse of battery from which we draw molecules. Linear polarization experiment shows that the Zn- P/PEG
energy in the form of electrons by the oxidative process i.e. discharge electrode had a corrosion potential of − 0.764 V suggesting that it ex
process. Passivation is the term used to describe an electrode that cannot hibits lower corrosion reactivity as compared
be further discharged due to the formation of an insulating film on its with the Zn-P electrode (0.916 V) (Fig. 15 (a)). While cyclic charge-
surface that blocks migration of the discharge product and/or OH− ions. discharge measurements, the Zn-P-based symmetrical cell had less
Not only the discharge process, the charging process at the anode also overpotential and only exhibited stability for 200 hours, but the Zn-P/
plays important role for revert back Zn in zero oxidation in the form of PEG symmetric cell showed stability for 1000 hours at 5 mA cm− 2
Zn plating. However, there are few issues associated with the reversible with no change in the voltage gap. When the current density reaches
conversion of Zn during charging and discharging cycles. The major 50 mA cm− 2, Zn-P’s cycling stability further declines and is only stable
processes that affect the reversibility are dendrite growth over Zn anode, for 50 hours. Nevertheless, the Zn-P/PEG symmetrical cell have cycling
ZnO formation and hydrogen evolution reaction (HER). When a zinc stability for 300 hours. To study the mechanism behind the stability of
electrode is discharged and the Zn(OH)2− 4 discharge product has reached Zn-P/PEG anode, post battery SEM studies were performed to see the
its solubility limit, ZnO is precipitated on the electrode surface. Due to changes in the anode morphology. After 25 cycles, Zn-P shows irregular
this. ZnO gets deposited as a thin film on zinc electrode inhibits the spherical structure whereas Zn-P/PEG samples showed a regularly
further discharge of zinc electrode. This causes a major limitation during hexagonal stacked structure which may contribute towards a regulative
the recharging of the zinc-air batteries. There is unavoidable formation effect in Zn deposition (Fig. 15 (b)). Pristine graphene and reduced
of insoluble ZnO in the electrolyte and electrode due to the dispropor graphene oxide had also been used for surface modification of zinc, used
tionate reaction of zincate ion (Zn(OH)2)4- creates severe hinderance on for suppressing dendrite growth by using electrostatic self-assembly
the rechargeability of the battery. This ZnO forms irreversible passiv techniques[175,176]. Use of binders to make a continuous network
ating layer, that blocks the access to the bulk anode in participating in can cause decline in activity, furthermore, electrode prepared by these
discharge process (Fig. 14 (a)). Dendrite formation during charging methods are microscopically uneven, leading to a “tip effect”. Wang, J.
process is another problem Zn anode suffers from (Fig. 14 (b)). During et.al prepared a Zn matrix composite anode through 3D carbon network
plating process, non-uniform electric field at the interface of anode and by powder metallurgy to reduce the internal resistance due to the
electrolyte renders the uniform deposition of zinc, which appears in the absence of continuous network in the composite as shown in Fig. 15 (c).
form of spike-like protrusions, and puncture the separator and causes the In order to access the corrosion performance of the Zn@C composite
short circuit. Although the mechanism of dendritic growth is not fully electrode, a series of corrosion potential tests were conducted. Zn@C-5
known, it is believed that it follows three steps (1) liquid-phase mass showed the highest corrosion potential alongside the smallest corrosion
transfer (Zn2+ ion diffusion), (2) charge transfer (Zn2+ ion reduction), current during the evaluation (Fig. 15 (d)), thereby indicating its
Table 2
The recently reported polymer-based electrolyte along with their different physical properties for ZAB.
Sr. No. Solid state electrolyte Ionic conductivity Water retention(%) Power density Cycling time Ref
1 PAM/CS-BT-KBr 110.5mScm− 1 _ 153 mW cm− 2 150 h at 2mAcm− 2 [153]

2 C@LC HPE 234mScm− 1 _ 141.55 mW cm− 2 65 h at 0.5mAcm− 2 [154]
3 PANa/CNF/GONR 268mScm− 1 _ 90.7 mW cm− 2 323 h at 2mAcm− 2 [155]
4 G-PBA/PAAm SPDH 219mScm− 1 70.6 % After 7 days 46 mW cm− 2 35 h at 1mAcm− 2 [156]
5 PVA/PEG 42.5mScm− 1 _ 109 mW cm− 2 46 h at 5mAcm− 2 [146]
6 PANa/CNF/GO 178.6mScm− 1 _ _ 214 h at 2mAcm− 2 [157]
7 PVA-PANa-ACG-KI 283.7mScm− 1 73.4 % After 36 h 47.97 mW cm− 2 62 h at 0.5mAcm− 2 [158]
8 AEPEM-GF 9.0×10− 2Scm− 1 _ 140 mW cm− 2 14 h at 2mAcm− 2 [159]
9 QASA 5.23×10− 2Scm− 1 _ 57.28 mW cm− 2 38 h at 0.5mAcm− 2 [160]
10 PCG 13mScm− 1 _ 128 mW cm− 2 30 h at 2mAcm− 2 [161]
20
Fig. 14. (a) Cause of failures due to the repetitive cycling of the rechargeable zinc-air battery (b) Schematic showing the mechanism of zinc dendrite formation.
Fig. 15. (a) Tafel polarization curves of Zn-P and Zn-P/PEG (b) Post-battery Sem images of Zn-P and Zn-P/PEG. Copyright with permission from Elsevier (2023)
[172] (c) Preparation Process of Zn@C (d) Tafel curves showing the corrosion on Zn@C-5, Zn-p and Zn foil (e) Galvanostatic Zn plating/stripping curves in sym
metrical cells for Zn@C-5, Zn-p and Zn foil at a current density of 1 mAcm-2. Copyright with permission from Wiley-VCH (2024) [173] (f) Schematic showing Zn
plating process on (a) the pristine Zn foil electrode with a native passivation layer and (b) the 3D r-Zn foil electrode with a clean surface. Copyright with permission
from ACS (2020) [174].
superior corrosion resistance. The enhanced corrosion resistance can be stripping behavior. Many attempts have been made to make allow of
ascribed to the encapsulation of the particles by the carbon layer, which zinc with various metals like Cu, Al, Ag etc[177–179]. to improve its
prevents the direct interactions between the Zn and electrolyte. The performance. Peng, Y et al. prepared Zn-Sn alloy via powder sintering
assembled Zn air battery shows a power density of 111. 5 mW cm− 2 with technique for low dendrite growth and to promote corrosion resistant.
Zn@C-5 as anode which is higher than Zn-p (94.2 mW cm− 2) and Zn foil Alloy formation promotes the reversibility of stripping/plating of zinc
(62.6 mW cm− 2)[173]. without the formation of dendrites which was expected due to the
Recently, alloy materials have received great attention due to their regulated electron density and charge distribution of electrode as sug
higher ionic conductivity, thus favoring rapid, unhindered ion transfer gested by theoretical calculations. On the other hand, the abundant and
kinetics across the interface thereby facilitating uniform deposition/ rigid ZnSn interphase can still maintained the chemically stability which
21
resist the corrosion. The long-term cycling performance at 0.5 mA cm− 2 [184]. These results indicate that the CNF electrolyte adversely affects
shows low overpotential for Zn-Sn plate as compared to the zinc foil. the hydrogen evolution reaction (HER) performance of Pt/C, both from
After the introduction of small amount of Sn the dendrite formation is a thermodynamic (increase in HER onset potential and overpotential) as
lowered, even after the 400 h the surface of electrode remained almost well as a kinetic perspective (reduction in the HER current density).
dendrite-free. Further, ZAB analysis shows that Zn-Sn10 alloy shows an
OCV of 1.546 V which is higher than that of pure Zn as anode (1.323 V). 5. Device
Maximum power density output using Zn-Sn10 anode comes out
100 mW cm− 2 which is more than that of pure Zn based battery The 140-year history of zinc-air batteries represents a remarkable
(50 mW cm− 2)[180]. The creation of the ZnO passivation layer on the journey within the realm of battery evolution. Various efforts have been
tropological surface causes the ordinary Zn foil’s surface to become made by different scientific communities to improve the ZAB perfor
uneven. The passivation layer that forms on the anode during the plat mance by developing different materials for cathode, anode, and elec
ing/stripping process creates a barrier to charge transmission. Due to the trolyte respectively. However, there is a gap in the structural design of
inhomogeneity on the zinc anode’s surface, the anode’s accessible area ZABs that still exists which should be improved for its use in various
to the electrolyte is hampered, and the development of dendrites causes applications. The open-cell design of zinc-air battery for the passage of
a battery short circuit. Thus, designing the zinc anode without a oxygen has a real disadvantage of aqueous ZAB due to the leakage of
passivation layer is crucial for extending the life of zinc air batteries. electrolyte, furthermore, to serves as a compatible power source for
Thus, using the chemical etching technique combined with ultra wearable electronic devices, flexible model for ZABs, capable of main
sonication, Wang, J et al. created a three-dimensional ridge-like zinc taining stability in complex wearable application scenarios, where it
(r-Zn)[174]. The chemical etching process produces clean and ridge-like may face possible short-circuit, and fracture under bending, twisting,
structure which is beneficial for uniform plating/stripping process due stretching and other forms of deformations. The advanced sophisticated
to uniform electric field around Zn anode (Fig. 15 (f)). Along with the electrode configurations employed in F-ZABs reported in recent years
increase in surface area, the ridge-like structure also inhibits the for can be divided into three specific categories, namely sandwich-type,
mation dendritic growth. The chemical etching of Zn foil reduces the cable/fiber-type, and coplanar-type.
proportion of growth of hexagonal Zn along (002) plane. The electro
chemical performance of the r-Zn and Zn foil were tested in symmetric 5.1. Sandwich-type F-ZABs
cells. The r-Zn shows the stable plating/stripping behavior for 400 h at
1 mA cm− 2 with low overpotential of 26 mV while the commercial Zn This is the most common type of flexible rechargeable zinc-air bat
foil only stable upto 180 h with a high overpotential of 76 mV. The post tery. It is having the simplest design which consists of zinc, electrolyte,
catalytic SEM shows that the Zn metal is not uniformly plated on the and cathode. A layer of polymer electrolyte is packed between the anode
surface of pristine zinc while the r-Zn maintained its morphology shows and cathode (Fig. 16 (a)). This framework is suitable for large-scale and
that Zn is uniformly plated. Lately, scientists have been working on economical viable production of RZAB. Su, C.Y., et al. fabricated a
creating a three-dimensional zinc anode to extend the life of secondary sandwich model of flexible solid-state device using N-GCNT/FeCo-3 as
batteries and prevent undesired dendrite formation. The 3D modified bi-functional electrocatalyst, Fig. 17(b) shows the stable cyclic galva
zinc shows an aggregated morphology which could prevent the dendrite nostatic charge-discharge behavior under different bending positions
formation during stripping/plating process. The as-assembled zinc air (Fig. 17 (b)[187]. Chen, Z., et al. fabricated flexible ZAB using Zn foil as
battery, its specific capacity and power density for 3D-modified zinc are anode while the mixture of Pt/C and RuO2 as air cathode with
676 mAh gZn− 1, 75 mW cm− 2, whereas for unmodified zinc, they are HAcc@HPPANCOONa/PANa as quasi solid electrolytes (QSEs). The
only 505 mAh gZn− 1, 41 mW cm− 2. The galvanostatic charge-discharge fabricated FZAB shows high stability for 100 h with high power density
curve displayed at various density of discharge values, ranging from 5 % of 126 mW cm− 2. Further the Galvanostatic cycles conducted for FZAB
to 20 % at 25 mA cm–2. Up to 70 hours at various discharge densities, at different angles form 0◦ , 45◦ and 90◦ shows extremely stability with
the modified ZABs exhibit no voltage variation. The unchanged ZAB, on the bending test. A pulse sensor is used to measure people’s heartbeats
the other hand, is only stable over a 30-hour cycle procedure. After 40 and pulses can be run by connecting the three FZAB with HAcc@HP
cycles at various discharge densities, the modified zinc does not develop PANCOONa/PANa QSEs in series[145]. Li, W., et al. shows the practical
dendrites, indicating the dendritic growth formation could be sup application of ZAB by developing both button type and sandwich type
pressed[181]. As already mentioned above, HER is another problem solid-state flexible ZAB with PVAA-Cellulose as an electrolyte. Further,
associated with the zinc anode due to its lower reduction potential of the flexible ZAB can shows stable charge-discharge behavior up to 54 h
Zn/ZnO (-1.25 V vs SHE) than that of HER (-0.83 V vs SHE). Due to the with highest specific capacity of 724 mAh g−Zn1. The sandwich type
corrosive nature of HER, the performance and cyclic stability of zinc-air flexible ZAB shows open circuit voltage of 1.41 V which can drive a fan
battery are compromised. Shifting the onset of HER at higher potential at different bending angles 0◦ , 90◦ and 180◦ [143]. Cai, S., et al. prepared
could mitigate the corrosion problem associated with zinc-air batteries. a porous poly(vinyl alcohol)/poly(ethylene glycol) (PVA/PEG) quasi
Additives like heavy metal (Cd/Hg) or a metal oxide (Al2O3/In2O3/ solid state electrolyte which then fabricated for a flexible ZAB with
Bi2O3) in electrolyte with high reduction potential can increase the onset commercial MnO2 as air cathode. The Galvanostatic charge discharge
potential for HER[182]. Subramaniam, T., et al. have used this nano performance of FZAB were evaluated at different angles 0◦ and 90◦ the
fluid- based strategy to increase the onset potential of HER. They have voltage plateu shows no change at different bending angles. To check the
used nanofluid with 0.1 wt% of SiOx (SNF) and 0.1 wt% ZnO (ZNF) to practical application of FZAB, four batteries were connected in series to
mitigate HER. LSV plot with Pt/C as electrocatalyst shows the increase run a fan, to charge small electronics and could light a small bulb also
in onset potential of HER with the addition of SiOx and ZnO in the [146]. Jiao, M., et al. fabricated ZAB using NiMnCo- activated carbon
electrolyte. Same effect can be observed through the increase of the tafel (NiMnCo-AC) as a cathode material with PVA-KOH as gel electrolyte and
slop from 45 mV dec− 1 to 145 and 172 mV dec− 1 for SNF and ZNF Zn foil as anode. The fabricated ZAB shows OCP of 1.377 V and 1.380 V
electrolytes, respectively indicating the decrease in HER process.The at normal and bending position respectively. Further, the three batteries
cyclic performance of ZAB is also enhanced with nanofluid electrolyte connected in series can charge a smartphone and can also glow a LED
from 4 to 10 hours[183]. Subramaniam, T., et al. again adopted this scroller (Fig. 17 (c))[188].
nanofluid strategy to suppress the HER by adding carbon nanodots in the
native 6 M electrolyte. The addition of CNDs in 6 M KOH not only in 5.2. Cable/fiber-type F-ZABs
creases the onset potential of HER but also increases the tafel slop from
52 mV dec− 1 (native electrolyte) to 210 mV dec− 1 (CNF electrolyte) Cable type or fibre type, an another class of widely used structural
22
Fig. 16. (a) Structural design of flexible (a) sandwich, (b) cable. Copyright with permission from Wiley-VCH (2015) [185], (d) coplanar, and (e) on-chip integrated
configurations. Reproduced from Wiley-VCH (2023) [186].
Fig. 17. (a) Optical image showing the assembled sandwitch type zinc air battery (b) Galvanostatic discharge-charge profile of FZABs under bending angles of 0, 45,
and 90◦ bending using N-GCNT/FeCo-3 as cathode material. Copyright with permission from Wiley-VCH (2017) [187]. (c) Three sandwich type Zinc-air battery
glowing LED with TBSI signal and demonstrating the charging of a smartphone. Reproduced from AAAS (2022) [188]. (d) Galvanostatic discharge and charge
characteristics of the cable-type ZAB under diverse conditions. Copyright with permission from Wiley-VCH (2020) [189]. (e-f) Image depicting knittable FAZABs
powering a wearable flexible light emitting diode display. Copyright with permission from Wiley-VCH (2023) [190]. (g) Discharge curve and corresponding power
density. Copyright with permission from Elsevier (2022) [191]. (h) Open-circuit potential curves and (i) polarization curves with their corresponding power plots of
four individual coplanar devices arranged in parallel. Copyright with permission from ACS (2023) [192].
23
design for rechargeable F-ZAB. To prepare these cable type batteries, a 6. Conclusion
Zn spring or flexible rod is used as anode. On top of zinc anode, gel
electrolyte solution is drop-casted and then allowed to aged followed by For the rapid demand for next generation energy storage devices,
wrapping with air cathode and packaged with breathable tape to pass with high-energy efficiency and safe operational mechanisms, ZABs
the air (Fig. 16 (b)). There is one big advantage of these cable-type theoretically fulfill the requirements, which puts them as potentially
batteries over sandwich models that they possess excellent multidirec compatible energy storage technology. This review discussed zinc-air
tional flexibility, therefore they can to integrated into clothing to batteries’ basic principles and mechanisms followed by their associ
energize wearable devices under various deformation circumstances. ated problems. Problems associated with each component and strategies
Song, Z., et al. fabricated cable type ZAB by using KI–PVAA–GO gel to solve these problems were discussed in detail. In each section, we
polymer electrolyte, Zinc wire as anode, and Pt/C + Co3O4 slurry on focused on the mechanism and the chemistry behind the improvement
carbon fibers as cathode. Galvanostatic charge-discharge measurement in the performance. Recent advancements especially from the past 4
for cable type shows stable behavior under different conditions (i.e., a years have been discussed thoroughly. In case of the cathode, the dis
line and a line with one knot or two knots) (Fig. 17 (d)). In addition, cussion was centered on enhancement in the bifunctional activity of the
three cable-type batteries were connected in series to power up a catalyst by modulating with the eg occupancy, generating dual active
smartwatch[189]. Fan, X., et al.synthesized sulfonate functionalized side for bi-functionality and through “atom-economic” single atom
nanocomposite QSGPE (quasi-solid-state gel polymer electrolyte) to catalysis preparation strategies. Electrolyte, which is clearly a hot topic
fabricate wire-type FAZAB. Zinc wire and Co3O4 used as anode and for many battery technologies, as it’s a direct source for the communi
cathode respectively. The fabricated wire-FAZABs demonstrated excel cation between both electrodes. This part discusses how and why elec
lent cyclic stability as it can withstand deformation under various trolyte generation got moved from liquid to gel polymer electrolyte for
bending angles (e.g., 45◦ , 90◦ , 135◦ , 180◦ ). Real life experience were energy application. We discussed the recent progress and structural
shown using three wire-shaped FAZABs connected in series which were design of electrolytes for high ionic conductivity and mechanical sta
integrated into a knitted hat to power up a flexible light emitted diode bility etc. For anode, methods to suppress dendritic growth and the re
screen (Fig. 17 (e-f)) and a wristwatch suggesting its good compatibility petitive utilization of bulk zinc for a longer cyclic period had been
and feasibility[190]. Further, Zhang, P., et al.developed a novel cable explored. For the future perspective, this review article not only dis
fibrous zinc-air battery (F-ZAB) by employing a hollow fiber saturated cussed about the cathode design but also aimed to explain the issues
with aqueous potassium hydroxide as the electrolyte. It shows a large related to electrolyte and anode. A synergistic interaction between all
OCV of 1.45 V with a high peak density of 68.7 mWcm− 2 (Fig. 17 (g)), these three components in ZAB will surely pave the new pathways for
significant specific capacity of 754 mAhg−Zn1 at 1 mA cm− 2, and good successful commercialization of it, beyond lithium in future.
rechargeability of 24 cycles at the same current density of
1 mA cm− 2[191]. CRediT authorship contribution statement
5.3. Coplanar-type F-ZABs Arkaj Singh: Writing – original draft, Visualization, Validation, Data
curation, Conceptualization. Ravinder Sharma: Writing – original
Apart from above two designs for flexible rechargeable zinc air draft. Akriti Gautam: Writing – original draft. Bhavnish Kumar:
batteries, recently coplanar-type batteries were also reported. For Writing – original draft. Sneha Mittal: Writing – original draft. Aditi
fabricating coplanar F-ZAB, an air cathode infused with the catalyst and Halder: Writing – review & editing, Project administration.
a Zn anode are arranged on the solid-state electrolyte (SSE) in a coplanar
form (Fig. 16 (c-d)). This coplanar deployment of electrodes signifi
cantly reduces the inter-electrode space and facilitates charge transfer. Declaration of Competing Interest
The coplanar type design of electrodes are currently in high demand in
micro-supercapacitor industries. The coplanar designs provides on-chip The authors declare that they have no known competing financial
integration and mass production using circuit etching technology. In interests or personal relationships that could have appeared to influence
tegrated coplanar ZABs are more powerful and reliable micropower the work reported in this paper.
supply for wearable/implanted applications as compared to micro-
supercapacitors due to their high theoretical energy density and ca Acknowledgments
pacity. Fang, W., et al. fabricated a coplanar flexible zinc air battery with
a air cathode Co–Fe–S@NSRPC loaded on thin carbon paper serving as The authors would like to thank the Ministry of Education of India
bifunctional electrocatalyst, zinc foil as anode while the polyacrylamide for financial support.
polyacrylic acid (PAM-PAA) dissolved in 6 M KOH as electrolyte. The
fabricated ZAB shows a peak power density of 78 mW cm− 2 while the Data availability
specific capacity at 5 mA cm− 2 current density is 785 mAh g− 1. The
charge-discharge cycle at flat, folded, bent, S shaped and twisted re This is a review article.
mains constant with no change in the voltage gap. The practical appli
cation of flexible 2D coplanar type ZAB shows running of electronic References
clock at different bending position of ZAB[193]. Coplanar type
solid-state zinc-air microbattery (ZAmB) was fabricated by Liu, G., et al. [1] B. Propfe, et al., Market penetration analysis of electric vehicles in the German
utilizing a simple 3D printing technique where Co3O4 acting as the passenger car market towards 2030, Int. J. Hydrog. Energy 38 (13) (2013)
5201–5208.
cathode and zinc foil as the anode. Four separate batteries are joined in [2] O. Egbue, S. Long, Barriers to widespread adoption of electric vehicles: An
series to form the coplanar integrated ZAmB. Compared to a single analysis of consumer attitudes and perceptions, Energy Policy 48 (2012)
battery module (1.37 V), the combined ZAmB’s OCP is 5.43 V, or 717–729.
[3] B. Dunn, H. Kamath, J.-M. Tarascon, Electrical energy storage for the grid: a
roughly 4 times higher (Fig. 17 (h)). When compared to a single battery
battery of choices, Science 334 (6058) (2011) 928–935.
(19.2 mW), the peak power density of a composite battery is 4 times [4] J.B. Goodenough, Y. Kim, Challenges for rechargeable Li batteries, Chem. Mater.
higher then a single ZAmB 76.4 mW (Fig 17 (i)). The PET 22 (3) (2010) 587–603.
surface-printed integrated ZAmB has the ability to illuminate an LED. [5] J.-M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium
batteries, nature 414 (6861) (2001) 359–367.
The figure illustrates how a smartphone can be charged using the ZAmB [6] G. Girishkumar, et al., Lithium− air battery: promise and challenges, J. Phys.
module printed on a cloth surface[192]. Chem. Lett. 1 (14) (2010) 2193–2203.
24
[7] J.S. Lee, et al., Metal–air batteries with high energy density: Li–air versus Zn–air, [45] J. Chen, et al., Dual single-atomic Ni-N4 and Fe-N4 sites constructing Janus
Adv. Energy Mater. 1 (1) (2011) 34–50. hollow graphene for selective oxygen electrocatalysis, Adv. Mater. 32 (30) (2020)
[8] P. Gu, et al., Rechargeable zinc–air batteries: a promising way to green energy, 2003134.
J. Mater. Chem. A 5 (17) (2017) 7651–7666. [46] C. Zhou, et al., Superdurable bifunctional oxygen electrocatalyst for high-
[9] X. Ren, Y. Wu, A low-overpotential potassium–oxygen battery based on performance zinc–air batteries, J. Am. Chem. Soc. 144 (6) (2022) 2694–2704.
potassium superoxide, J. Am. Chem. Soc. 135 (8) (2013) 2923–2926. [47] J. Shin, et al., Functionalized carbon dots on graphene as outstanding non-metal
[10] Z.-L. Wang, et al., Oxygen electrocatalysts in metal–air batteries: from aqueous to bifunctional oxygen electrocatalyst, Small 15 (16) (2019) 1900296.
nonaqueous electrolytes, Chem. Soc. Rev. 43 (22) (2014) 7746–7786. [48] L. She, et al., On the durability of iridium-based electrocatalysts toward the
[11] M.A. Rahman, X. Wang, C. Wen, High energy density metal-air batteries: a oxygen evolution reaction under acid environment, Adv. Funct. Mater. 32 (5)
review, J. Electrochem. Soc. 160 (10) (2013) A1759. (2022) 2108465.
[12] E.A. Schumacher, G.W. Heise, The alkaline cell with copper oxide or air [49] X. Liu, et al., Recent advances in the comprehension and regulation of lattice
depolarization (1902-1952), J. Electrochem. Soc. 99 (1952) 191C–196C. oxygen oxidation mechanism in oxygen evolution reaction, Trans. Tianjin Univ.
[13] S. Müller, et al., Development of rechargeable monopolar and bipolar zinc/air 29 (4) (2023) 247–253.
batteries, Chimia 49 (1-2) (1995), p. 27-27. [50] T. Zhou, et al., Asymmetrical Ru–O–Mn bridge active sites fully decouple
[14] P. Bonnick, J. Dahn, A simple coin cell design for testing rechargeable zinc-air or bifunctional oxygen electrocatalysis for rechargeable zinc-air batteries, ACS
alkaline battery systems, J. Electrochem. Soc. 159 (7) (2012) A981. Catal. 14 (2024) 9313–9322.
[15] A. Weidenkaff, S.G. Ebbinghaus, T. Lippert, Ln1-x A x CoO3 (Ln= Er, La; A= Ca, [51] Y.J. Li, et al., Multiscale structural engineering of Ni-doped CoO nanosheets for
Sr)/carbon nanotube composite materials applied for rechargeable Zn/air zinc–air batteries with high power density, Adv. Mater. 30 (46) (2018) 1804653.
batteries, Chem. Mater. 14 (4) (2002) 1797–1805. [52] M. Kuang, et al., CuCoO x/FeOOH Core–shell nanowires as an efficient
[16] Z.P. Cano, et al., Batteries and fuel cells for emerging electric vehicle markets, bifunctional oxygen evolution and reduction catalyst, ACS Energy Lett. 2 (10)
Nat. Energy 3 (4) (2018) 279–289. (2017) 2498–2505.
[17] G. Berckmans, et al., Cost projection of state of the art lithium-ion batteries for [53] C. Lin, et al., In situ directional formation of Co@ CoO x-embedded 1D carbon
electric vehicles up to 2030, Energies 10 (9) (2017) 1314. nanotubes as an efficient oxygen electrocatalyst for ultra-high rate Zn–air
[18] F. Cheng, J. Chen, Metal–air batteries: from oxygen reduction electrochemistry to batteries, J. Mater. Chem. A 5 (27) (2017) 13994–14002.
cathode catalysts, Chem. Soc. Rev. 41 (6) (2012) 2172–2192. [54] X. Guo, et al., Controllable solid-phase fabrication of an Fe2O3/Fe5C2/Fe–N–C
[19] Y. Li, H. Dai, Recent advances in zinc–air batteries, Chem. Soc. Rev. 43 (15) electrocatalyst toward optimizing the oxygen reduction reaction in zinc–air
(2014) 5257–5275. batteries, Nano Lett. 22 (12) (2022) 4879–4887.
[20] X. Cai, et al., Recent advances in air electrodes for Zn–air batteries: [55] T. Tang, et al., Metastable rock salt oxide-mediated synthesis of high-density
electrocatalysis and structural design, Mater. Horiz. 4 (6) (2017) 945–976. dual-protected M@ NC for long-life rechargeable zinc–air batteries with record
[21] J. Pan, et al., Advanced architectures and relatives of air electrodes in Zn–air power density, J. Am. Chem. Soc. 142 (15) (2020) 7116–7127.
batteries, Adv. Sci. 5 (4) (2018) 1700691. [56] Z. Guo, et al., Synergistic effect of Co and Fe bimetallic oxides/hydroxides
[22] S.K. Yadav, D. Deckenbach, J.J. Schneider, Secondary zinc–air batteries: a view composite structure as a bifunctional electrocatalyst for enhancing overall water
on rechargeability aspects, Batteries 8 (11) (2022) 244. splitting performance, J. Alloy. Compd. 895 (2022) 162614.
[23] X. Xie, et al., Recent advances in bifunctional dual-sites single-atom catalysts for [57] W.-J. Jiang, et al., Synergistic modulation of non-precious-metal electrocatalysts
oxygen electrocatalysis toward rechargeable zinc-air batteries, Sci. Bull. (2023). for advanced water splitting, Acc. Chem. Res. 53 (6) (2020) 1111–1123.
[24] X. Yan, Y. Ha, R. Wu, Binder-free air electrodes for rechargeable zinc-air batteries: [58] L. Peng, et al., Dual-ligand synergistic modulation: a satisfactory strategy for
recent progress and future perspectives, Small Methods 5 (4) (2021) 2000827. simultaneously improving the activity and stability of oxygen evolution
[25] Q. Liu, L. Wang, H. Fu, Research progress on the construction of synergistic electrocatalysts, Acs Catal. 7 (12) (2017) 8184–8191.
electrocatalytic ORR/OER self-supporting cathodes for zinc–air batteries, [59] S. Yuan, et al., Dual synergistic effects between Co and Mo2C in Co/Mo2C
J. Mater. Chem. A 11 (9) (2023) 4400–4427. heterostructure for electrocatalytic overall water splitting, Chem. Eng. J. 430
[26] X. Chen, et al., Recent advances in materials and design of electrochemically (2022) 132697.
rechargeable zinc–air batteries, Small 14 (44) (2018) 1801929. [60] Y. Niu, et al., A" trimurti" heterostructured hybrid with an intimate CoO/Co x P
[27] R. Cao, et al., Recent progress in non-precious catalysts for metal-air batteries, interface as a robust bifunctional air electrode for rechargeable Zn–air batteries,
Adv. Energy Mater. 2 (7) (2012) 816–829. J. Mater. Chem. A 8 (18) (2020) 9177–9184.
[28] V. Caramia, B. Bozzini, Materials science aspects of zinc–air batteries: a review, [61] P. Chen, et al., Metallic Co4N porous nanowire arrays activated by surface
Mater. Renew. Sustain. Energy 3 (2014) 1–12. oxidation as electrocatalysts for 455 the oxygen evolution reaction, 454, Angew.
[29] Z.W. Seh, et al., Combining theory and experiment in electrocatalysis: insights Chem. Int. Ed. 54 (2015) 14710–14714.
into materials design, Science 355 (6321) (2017) eaad4998. [62] E. Fabbri, et al., Dynamic surface self-reconstruction is the key of highly active
[30] J. Hwang, et al., Perovskites in catalysis and electrocatalysis, Science 358 (6364) perovskite nano-electrocatalysts for water splitting, Nat. Mater. 16 (9) (2017)
(2017) 751–756. 925–931.
[31] P. Christensen, A. Hamnett, D. Linares-Moya, Oxygen reduction and fuel [63] H. Jiang, et al., Structural self-reconstruction of catalysts in electrocatalysis, Acc.
oxidation in alkaline solution, Phys. Chem. Chem. Phys. 13 (12) (2011) Chem. Res. 51 (11) (2018) 2968–2977.
5206–5214. [64] M. Wu, et al., Self-reconstruction of Co/Co2P heterojunctions confined in N-
[32] C. Zinola, et al., A quantum chemical approach to the influence of platinum doped carbon nanotubes for Zinc–Air flow batteries, ACS Energy Lett. 6 (4)
surface structure on the oxygen electroreduction reaction, J. Phys. Chem. 98 (31) (2021) 1153–1161.
(1994) 7566–7576. [65] Z. Li, et al., Interfacial engineering of cobalt phosphide heterostructures confined
[33] J.K. Nørskov, et al., Origin of the overpotential for oxygen reduction at a fuel-cell in N, P-doped carbon for efficient bifunctional electrocatalysis in Zn–air batteries,
cathode, J. Phys. Chem. B 108 (46) (2004) 17886–17892. Inorg. Chem. Front. 11 (2) (2024) 549–561.
[34] A. Mathur, A. Halder, One-step synthesis of bifunctional iron-doped manganese [66] Y.-P. Deng, et al., Reconstructing 3D-metal electrocatalysts through anionic
oxide nanorods for rechargeable zinc–air batteries, Catal. Sci. Technol. 9 (5) evolution in zinc–air batteries, J. Am. Chem. Soc. 145 (37) (2023) 20248–20260.
(2019) 1245–1254. [67] X. Xu, et al., Modulation of PHase Transition in Cobalt Selenide with
[35] A. Mathur, et al., Surface engineering of 2D layered MnO2 with co-doping of Ni Simultaneous Construction of Heterojunctions for Highly-efficient Oxygen
and Fe for rechargeable zinc-air battery, J. Energy Storage 74 (2023) 109350. Electrocatalysis in Zinc–air Battery, Adv. Mater. 36 (8) (2024) 2306844.
[36] J. Suntivich, et al., A perovskite oxide optimized for oxygen evolution catalysis [68] M. Cui, et al., Graphdiyne-induced CoN/CoS2 heterojunction: boosting efficiency
from molecular orbital principles, Science 334 (6061) (2011) 1383–1385. for bifunctional oxygen electrochemistry in zinc-air batteries, ChemSusChem
[37] C. Wei, et al., Cations in octahedral sites: a descriptor for oxygen electrocatalysis (2024) e202400832.
on transition-metal spinels, Adv. Mater. 29 (23) (2017) 1606800. [69] Z. Niu, et al., Long-range regulation of Se doping for oxygen reduction of
[38] J. Suntivich, et al., Design principles for oxygen-reduction activity on perovskite atomically dispersed Sb catalysts for ultralow-temperature solid-state Zn–air
oxide catalysts for fuel cells and metal–air batteries, Nat. Chem. 3 (7) (2011) batteries, ACS Catal. 13 (10) (2023) 7122–7131.
546–550. [70] Z. Xu, et al., Synthesis of Ag–Ni–Fe–P multielemental nanoparticles as
[39] Y. Rao, et al., Optimizing the spin states of mesoporous Co3O4 nanorods through bifunctional oxygen reduction/evolution reaction electrocatalysts, ACS nano 15
vanadium doping for long-lasting and flexible rechargeable Zn–air batteries, ACS (4) (2021) 7131–7138.
Catal. 11 (13) (2021) 8097–8103. [71] T. Meng, et al., Double-atom dealloying-derived Frank partial dislocations in
[40] S. Liu, et al., Understanding the effect of nickel doping in cobalt spinel oxides on cobalt nanocatalysts boost metal–air batteries and fuel cells, Proc. Natl. Acad. Sci.
regulating spin state to promote the performance of the oxygen reduction 119 (45) (2022) e2214089119.
reaction and zinc–air batteries, ACS Energy Lett. 8 (1) (2022) 159–168. [72] Y. Wang, et al., Advanced electrocatalysts with single-metal-atom active sites,
[41] Q. Jing, et al., 3d orbital electron engineering in oxygen electrocatalyst for zinc- Chem. Rev. 120 (21) (2020) 12217–12314.
air batteries, Chem. Eng. J. 462 (2023) 142321. [73] C. Xie, et al., Surface and interface control in nanoparticle catalysis, Chem. Rev.
[42] Y. Sun, et al., Spin-related electron transfer and orbital interactions in oxygen 120 (2) (2019) 1184–1249.
electrocatalysis, Adv. Mater. 32 (39) (2020) 2003297. [74] L. Gloag, et al., Co-catalytic metal–support interactions in single-atom
[43] L. Yang, et al., Enhanced oxygen evolution and zinc-air battery performance via electrocatalysts, Nat. Rev. Mater. 9 (3) (2024) 173–189.
electronic spin modulation in heterostructured catalysts, Adv. Mater. (2024) [75] H. Xu, et al., Revisiting the universal principle for the rational design of single-
2400572. atom electrocatalysts, Nat. Catal. 7 (2) (2024) 207–218.
[44] H.-x Zhong, et al., In situ anchoring of Co9S8 nanoparticles on N and S co-doped [76] C. Zhu, et al., Single-atom electrocatalysts, Angew. Chem. Int. Ed. 56 (45) (2017)
porous carbon tube as bifunctional oxygen electrocatalysts, NPG Asia Mater. 8 (9) 13944–13960.
(2016) p. e308-e308.
25
[77] B. Qiao, et al., Single-atom catalysis of CO oxidation using Pt1/FeO x, Nat. Chem. [109] J. Liu, et al., Electronic tuning of core–shell CoNi nanoalloy/N-doped few-layer
3 (8) (2011) 634–641. graphene for efficient oxygen electrocatalysis in rechargeable zinc–air batteries,
[78] J. Li, et al., Challenges and perspectives of single-atom-based catalysts for J. Phys. Chem. Lett. 13 (29) (2022) 6743–6748.
electrochemical reactions, JACS Au 3 (3) (2023) 736–755. [110] X. Xie, et al., Tubular assemblies of N-doped carbon nanotubes loaded with NiFe
[79] Z. Lei, et al., Coordination modulation of iridium single-atom catalyst maximizing alloy nanoparticles as efficient bifunctional catalysts for rechargeable zinc-air
water oxidation activity, Nat. Commun. 13 (1) (2022) 24. batteries, Nanoscale 12 (24) (2020) 13129–13136.
[80] J. Shan, et al., Metal-metal interactions in correlated single-atom catalysts, Sci. [111] X. Chen, et al., Nanostructure engineering and electronic modulation of a PtNi
Adv. 8 (17) (2022) eabo0762. alloy catalyst for enhanced oxygen reduction electrocatalysis in zinc–air batteries,
[81] H.B. Zhang, et al., Bulk preparation of free-standing single-iron-atom catalysts J. Phys. Chem. Lett. 14 (7) (2023) 1740–1747.
directly as the air electrodes for high-performance zinc-air batteries, Carbon [112] C. You, et al., Rechargeable zinc–air battery with ultrahigh power density based
Energy 5 (5) (2023) e289. on uniform N, co codoped carbon nanospheres, ACS Appl. Mater. Interfaces 11
[82] Z.K. Yang, C.-Z. Yuan, A.-W. Xu, Confined pyrolysis within a nanochannel to form (47) (2019) 44153–44160.
a highly efficient single iron site catalyst for Zn–air batteries, ACS Energy Lett. 3 [113] K. Wang, et al., Modulation of ligand fields in a single-atom site by the molten salt
(10) (2018) 2383–2389. strategy for enhanced oxygen bifunctional activity for zinc-air batteries, ACS nano
[83] Y. Wang, et al., Directional manipulation of electron transfer by energy level 16 (8) (2022) 11944–11956.
engineering for efficient cathodic oxygen reduction, Nano Lett. 22 (16) (2022) [114] K. Ding, et al., Confined N-CoSe2 active sites boost bifunctional oxygen
6622–6630. electrocatalysis for rechargeable Zn–air batteries, Nano Energy 91 (2022)
[84] G. Kumar, et al., Pd “kills two birds with one stone” for the synthesis of catalyst: 106675.
dual active sites of Pd triggers the kinetics of O2 electrocatalysis, Small 20 (9) [115] N. Thakur, et al., Nickel iron phosphide/phosphate as an oxygen bifunctional
(2024) 2307110. electrocatalyst for high-power-density rechargeable Zn–air batteries. ACS Appl.
[85] K. Chen, et al., Iron phthalocyanine with coordination induced electronic Mater. Interfaces 13 (44) (2021) 52487–52497.
localization to boost oxygen reduction reaction, Nat. Commun. 11 (1) (2020) [116] H. Hu, et al., Bifunctional oxygen electrocatalysts enriched with single Fe atoms
4173. and NiFe2O4 nanoparticles for rechargeable zinc–air batteries, Energy Storage
[86] J.H. Zagal, M.T. Koper, Reactivity descriptors for the activity of molecular MN4 Mater. 54 (2023) 517–523.
catalysts for the oxygen reduction reaction, Angew. Chem. Int. Ed. 55 (47) (2016) [117] Y. Niu, et al., Engineering two-phase bifunctional oxygen electrocatalysts with
14510–14521. tunable and synergetic components for flexible Zn–air batteries, Nano-Micro Lett.
[87] J.P. Collman, et al., Catalytic reduction of O2 by cytochrome c using a synthetic 13 (1) (2021) 126.
model of cytochrome c oxidase, J. Am. Chem. Soc. 131 (14) (2009) 5034–5035. [118] D.-H. Wu, et al., Noble metal-free FeCoNiMnV high entropy alloy anchored on N-
[88] S. Mukherjee, et al., A biosynthetic model of cytochrome c oxidase as an doped carbon nanotubes with prominent activity and durability for oxygen
electrocatalyst for oxygen reduction, Nat. Commun. 6 (1) (2015) 8467. reduction and zinc–air batteries, J. Colloid Interface Sci. 662 (2024) 149–159.
[89] P. Ei Phyu Win, et al., Molecular architectures of iron complexes for oxygen [119] X. Zheng, et al., A self-jet vapor-phase growth of 3D FeNi@ NCNT clusters as
reduction catalysis—Activity enhancement by hydroxide ions coupling, Proc. efficient oxygen electrocatalysts for zinc-air batteries, Small 17 (4) (2021)
Natl. Acad. Sci. 121 (11) (2024) e2316553121. 2006183.
[90] S. Sarkar, et al., Universal approach for electronically tuned transition-metal- [120] N.-F. Yu, et al., Highly efficient Co3O4/Co@ NCs bifunctional oxygen
doped graphitic carbon nitride as a conductive electrode material for highly electrocatalysts for long life rechargeable Zn-air batteries, Nano Energy 77 (2020)
efficient oxygen reduction reaction, Inorg. Chem. 59 (2) (2020) 1332–1339. 105200.
[91] S. Gong, et al., Designing highly efficient dual-metal single-atom electrocatalysts [121] X. Shi, et al., FeS2–CoS2 incorporated into nitrogen-doped carbon nanofibers to
for the oxygen reduction reaction inspired by biological enzyme systems, boost oxygen electrocatalysis for durable rechargeable Zn-air batteries. J. Power
J. Mater. Chem. A 6 (27) (2018) 13254–13262. Sources 482 (2021) 228955.
[92] Y.-j Wu, et al., Controlled synthesis of FeNx-CoNx dual active sites interfaced with [122] J. Liu, et al., FeCoNi nanoalloys embedded in hierarchical N-rich carbon matrix
metallic Co nanoparticles as bifunctional oxygen electrocatalysts for rechargeable with enhanced oxygen electrocatalysis for rechargeable Zn-air batteries, J. Mater.
Zn-air batteries, Appl. Catal. B: Environ. 278 (2020) 119259. Chem. A 9 (48) (2021) 27701–27708.
[93] S. Sarkar, et al., Strategic modulation of target-specific isolated Fe, Co single-atom [123] Z. Wu, et al., Sulfurated metal–organic framework-derived nanocomposites for
active sites for oxygen electrocatalysis impacting high power Zn–air battery, ACS efficient bifunctional oxygen electrocatalysis and rechargeable Zn–air battery.
nano 16 (5) (2022) 7890–7903. ACS Sustain. Chem. Eng. 8 (24) (2020) 9226–9234.
[94] Y. He, et al., Atomically dispersed Fe–Co dual metal sites as bifunctional oxygen [124] W. Sun, et al., One-step integration of CoNi phosphides in N, P co-doped carbons
electrocatalysts for rechargeable and flexible Zn–air batteries, ACS Catal. 12 (2) towards highly efficient oxygen electrocatalysis for rechargeable Zn-air battery,
(2022) 1216–1227. Appl. Surf. Sci. 554 (2021) 149670.
[95] G. Kumar, R.S. Dey, Coordination engineering of dual Co, Ni active sites in N- [125] W.W. Xie, et al., Formation of hollow frameworks of dual-sided Fe/Fe3C@ N-
doped carbon fostering reversible oxygen electrocatalysis, Inorg. Chem. 62 (33) doped carbon nanotubes as bifunctional oxygen electrocatalyst for Zn-air
(2023) 13519–13529. batteries, Appl. Catal. B: Environ. 317 (2022) 121760.
[96] F. Liu, et al., Simultaneously engineering the coordination environment and pore [126] X. He, et al., Engineering the electronic states of Ni 3 FeN via zinc ion regulation
architecture of metal–organic framework-derived single-atomic iron catalysts for for promoting oxygen electrocatalysis in rechargeable Zn–air batteries, J. Mater.
ultraefficient oxygen reduction, Small 17 (40) (2021) 2102425. Chem. A 9 (4) (2021) 2301–2307.
[97] G. Yasin, et al., Simultaneously engineering the synergistic-effects and [127] Y. Xiao, et al., A bimetallic MOF@ graphene oxide composite as an efficient
coordination-environment of dual-single-atomic iron/cobalt-sites as a bifunctional oxygen electrocatalyst for rechargeable Zn–air batteries, Dalton
bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries, ACS Catal. Trans. 49 (17) (2020) 5730–5735.
13 (4) (2023) 2313–2325. [128] Q. Lu, et al., Rich atomic interfaces between sub-1 nm RuOx clusters and porous
[98] H. Huang, et al., Clusters induced electron redistribution to tune oxygen Co3O4 nanosheets boost oxygen electrocatalysis bifunctionality for advanced Zn-
reduction activity of transition metal single-atom for metal–air batteries, Angew. air batteries, Energy Storage Mater. 32 (2020) 20–29.
Chem. 134 (12) (2022) e202116068. [129] J. Zhu, et al., A triphasic bifunctional oxygen electrocatalyst with tunable and
[99] F. Li, et al., Tin nanoclusters confined in nitrogenated carbon for the oxygen synergetic interfacial structure for rechargeable Zn-air batteries, Adv. Energy
reduction reaction, ACS Nano 16 (11) (2022) 18830–18837. Mater. 10 (4) (2020) 1903003.
[100] Z. Wang, et al., Understanding the synergistic effects of cobalt single atoms and [130] Y. Zhang, et al., Three-dimensionally ordered mesoporous Co3O4 decorated with
small nanoparticles: enhancing oxygen reduction reaction catalytic activity and Mg as bifunctional oxygen electrocatalysts for high-performance zinc-air
stability for zinc-air batteries, Adv. Funct. Mater. 31 (45) (2021) 2104735. batteries, Nano Energy 100 (2022) 107425.
[101] X. Wei, et al., Tuning the spin state of Fe single atoms by Pd nanoclusters enables [131] L. Wei, et al., Amorphous bimetallic oxide–graphene hybrids as bifunctional
robust oxygen reduction with dissociative pathway, Chem 9 (1) (2023) 181–197. oxygen electrocatalysts for rechargeable Zn–air batteries, Adv. Mater. 29 (38)
[102] S.N. Zhao, et al., Electronically and geometrically modified single-atom Fe sites (2017) 1701410.
by adjacent Fe nanoparticles for enhanced oxygen reduction, Adv. Mater. 34 (5) [132] S. Peng, et al., Electronic and defective engineering of electrospun CaMnO3
(2022) 2107291. nanotubes for enhanced oxygen electrocatalysis in rechargeable zinc–air
[103] Z. Wang, et al., Cooperation between dual metal atoms and nanoclusters enhances batteries, Adv. Energy Mater. 8 (22) (2018) 1800612.
activity and stability for oxygen reduction and evolution, ACS Nano 17 (9) (2023) [133] F. Li, J. Chen, Mechanistic evolution of aprotic lithium-oxygen batteries, Adv.
8622–8633. Energy Mater. 7 (24) (2017) 1602934.
[104] R. Luo, et al., Yttrium oxide nanoclusters boosted Fe-N4 and Fe4N electrocatalyst [134] A. Polman, et al., Photovoltaic materials: present efficiencies and future
for future zinc–air battery, Adv. Funct. Mater. 34 (11) (2024) 2311084. challenges, Science 352 (6283) (2016) aad4424.
[105] Z. Li, et al., Asymmetric coordination of bimetallic Fe–Co single-atom pairs [135] X. Fu, et al., Direct solar energy conversion on zinc–air battery, Proc. Natl. Acad.
toward enhanced bifunctional activity for rechargeable zinc–air batteries, ACS Sci. 121 (14) (2024) e2318777121.
nano (2024). [136] D. Zhu, et al., Photoinduced oxygen reduction reaction boosts the output voltage
[106] J. Zhong, et al., Engineering symmetry-breaking centers and d-orbital modulation of a zinc–air battery, Angew. Chem. 131 (36) (2019) 12590–12594.
in triatomic catalysts for zinc-air batteries, ACS nano 18 (7) (2024) 5258–5269. [137] C. Tomon, et al., Photoactive Zn–air batteries using spinel-type cobalt oxide as a
[107] C. Brea, G. Hu, Mechanistic insight into dual-metal-site catalysts for the oxygen bifunctional photocatalyst at the air cathode, Chem. Commun. 55 (42) (2019)
reduction reaction, ACS Catal. 13 (7) (2023) 4992–4999. 5855–5858.
[108] M. Liu, et al., Atomically dispersed metal catalysts for the oxygen reduction [138] A. Mathur, R. Kaushik, A. Halder, Photoenhanced performance of Cobalt-
reaction: synthesis, characterization, reaction mechanisms and electrochemical intercalated 2-D manganese oxide sheets for rechargeable zinc–air batteries.
energy applications, Energy Environ. Sci. 12 (10) (2019) 2890–2923. Mater. Today Energy 19 (2021) 100612.
26
[139] C. Wang, et al., Rechargeable zinc-air batteries with neutral electrolytes: Recent [167] C. Xie, et al., Issues and solutions toward zinc anode in aqueous zinc-ion batteries:
advances, challenges, and prospects, EnergyChem 3 (4) (2021) 100055. a mini review, Carbon Energy 2 (4) (2020) 540–560.
[140] F. Santos, et al., Structural modifications and ionic transport of PVA-KOH [168] Z. Xu, M. Wu, Toward dendrite-free deposition in zinc-based flow batteries: status
hydrogels applied in Zn/Air batteries, J. Electroanal. Chem. 850 (2019) 113380. and prospects, Batteries 8 (9) (2022) 117.
[141] M.E. Tuckerman, D. Marx, M. Parrinello, The nature and transport mechanism of [169] Q. Yang, et al., Do zinc dendrites exist in neutral zinc batteries: a developed
hydrated hydroxide ions in aqueous solution, Nature 417 (6892) (2002) 925–929. electrohealing strategy to in situ rescue in-service batteries, Adv. Mater. 31 (43)
[142] M.M. Abudabbus, et al., In situ electrochemical synthesis of silver-doped poly (2019) 1903778.
(vinyl alcohol)/graphene composite hydrogels and their physico-chemical and [170] Y. Yin, et al., Dendrite-free zinc deposition induced by tin-modified
thermal properties, Compos. Part B: Eng. 140 (2018) 99–107. multifunctional 3D host for stable zinc-based flow battery, Adv. Mater. 32 (6)
[143] W. Li, et al., Gel polymer-based composite solid-state electrolyte for long-cycle- (2020) 1906803.
life rechargeable zinc–air batteries, ACS Sustain. Chem. Eng. 11 (9) (2023) [171] Y. Zeng, et al., Dendrite-free zinc deposition induced by multifunctional CNT
3732–3739. frameworks for stable flexible Zn-ion batteries, Adv. Mater. 31 (36) (2019)
[144] H. Dou, et al., Bioinspired tough solid-state electrolyte for flexible ultralong-life 1903675.
zinc–air battery, Adv. Mater. 34 (18) (2022) 2110585. [172] X. Huyan, et al., Polyethylene glycol coating on zinc powder surface: Applications
[145] Z. Chen, et al., Enhanced semi-interpenetrating network quasi-solid electrolytes in dendrite-free zinc anodes with enhanced utilization rate, Appl. Surf. Sci. 614
modified by hollow porous nanofibers for flexible zinc–air batteries. ACS Sustain. (2023) 156209.
Chem. Eng. 11 (28) (2023) 10391–10401. [173] J. Wang, et al., In situ implanting 3D carbon network reinforced zinc composite
[146] S. Cai, et al., Ice-template-induced highly interconnected porous polymer gel by powder metallurgy for highly reversible Zn-based battery anodes, Angew.
electrolytes for dendrite-free flexible zinc–air batteries, J. Phys. Chem. Lett. 14 Chem. Int. Ed. 63 (10) (2024) e202318149.
(33) (2023) 7445–7453. [174] J. Wang, et al., A chemically polished zinc metal electrode with a ridge-like
[147] H. Dou, et al., Biomass solid-state electrolyte with abundant ion and water structure for cycle-stable aqueous batteries, ACS Appl. Mater. Interfaces 12 (20)
channels for flexible zinc–air batteries, Adv. Mater. (2024) 2401858. (2020) 23028–23034.
[148] Q. Liu, et al., Dual-network structured hydrogel electrolytes engaged solid-state [175] Y. Lin, et al., Binder-free freestanding 3D Zn-graphene anode induced from
rechargeable Zn-air/iodide hybrid batteries, Angew. Chem. Int. Ed. 61 (44) commercial zinc powders and graphene oxide for zinc ion battery with high
(2022) e202210567. utilization rate, ACS Appl. Energy Mater. 5 (12) (2022) 15222–15232.
[149] S. Wu, et al., Poly (vinyl alcohol) hydrogels with broad-range tunable mechanical [176] W. Du, et al., Enable commercial Zinc powders for dendrite-free Zinc anode with
properties via the Hofmeister effect, Adv. Mater. 33 (11) (2021) 2007829. improved utilization rate by pristine graphene hybridization, Energy Storage
[150] Z. Chen, et al., Locking water molecules loss of PAA hydrogel for flexible zinc-air Mater. 45 (2022) 465–473.
battery with NaCl doping, Adv. Funct. Mater. 33 (49) (2023) 2306223. [177] Z. Cai, et al., Chemically resistant Cu–Zn/Zn composite anode for long cycling
[151] X. Fan, et al., Porous nanocomposite gel polymer electrolyte with high ionic aqueous batteries, Energy Storage Mater. 27 (2020) 205–211.
conductivity and superior electrolyte retention capability for long-cycle-life [178] S.-B. Wang, et al., Lamella-nanostructured eutectic zinc–aluminum alloys as
flexible zinc–air batteries, Nano Energy 56 (2019) 454–462. reversible and dendrite-free anodes for aqueous rechargeable batteries, Nat.
[152] A. Singh, R. Sharma, A. Halder, Flexible solid-state Zn–air battery based on Commun. 11 (1) (2020) 1634.
polymer-oxygen-functionalized gC 3 N 4 composite membrane, Nanoscale 16 (8) [179] Y. Wang, et al., Uniform and dendrite-free zinc deposition enabled by in situ
(2024) 4157–4169. formed AgZn 3 for the zinc metal anode, J. Mater. Chem. A 9 (13) (2021)
[153] Z. Chen, et al., Enhanced zinc reversibility enabled by zinc–bromide complexation 8452–8461.
of a quasi-solid electrolyte for high-performance flexible zinc–air batteries, [180] Y. Peng, et al., Zn–Sn alloy anode with repressible dendrite grown and meliorative
J. Mater. Chem. A 12 (15) (2024) 8815–8825. corrosion resistance for Zn-air battery, J. Power Sources 526 (2022) 231173.
[154] Y. Zhang, et al., A lignocellulose-based hydrogel polymer electrolytes with high [181] J. Yu, et al., Ag-modified Cu foams as three-dimensional anodes for rechargeable
conductivity and stability for rechargeable flexible zinc-air batteries, J. Energy zinc–air batteries, ACS Appl. Nano Mater. 2 (5) (2019) 2679–2688.
Storage 95 (2024) 112644. [182] D.-J. Park, E.O. Aremu, K.-S. Ryu, Bismuth oxide as an excellent anode additive
[155] W. Liu, et al., Graphene oxide nanoribbon-based composite gel polymer for inhibiting dendrite formation in zinc-air secondary batteries, Appl. Surf. Sci.
electrolytes: enhancing mechanical strength and ionic conductivity for long 456 (2018) 507–514.
cycling lifetime of flexible zinc–air batteries, Energy Fuels 38 (7) (2024) [183] T. Subramaniam, et al., Mitigating hydrogen evolution reaction and corrosion of
6508–6517. zinc in electrically rechargeable zinc-air batteries using nanofluid electrolytes,
[156] X. Zhang, et al., Covalently cross-linked supramolecular-polymer dual-network J. Energy Storage 81 (2024) 110457.
hydrogel with high ionic conductivity and interfacial adhesion for wide [184] T. Subramaniam, et al., A rational approach to suppress hydrogen evolution
temperature-tolerant flexible zinc–air batteries, ACS Appl. Polym. Mater. 6 (9) reaction and its concurrent zinc corrosion in zinc-air batteries: a uniform
(2024) 5011–5020. dispersion of carbon nanodots in the electrolyte, J. Electrochem. Soc. 171 (5)
[157] W. Liu, et al., High-performance flexible zinc–air batteries enabled by a sodium (2024) 050503.
polyacrylate-based gel electrolyte containing graphene oxide and cellulose [185] J. Park, et al., All-solid-state cable-type flexible zinc-air battery, Adv. Mater. 27
nanofibers, Energy Fuels 37 (20) (2023) 16097–16104. (8) (2014) 1396–1401.
[158] X. Jia, et al., Gel polymer electrolyte with alkaline aquatic colloidal graphene for [186] H. Li, J. Chen, J. Fang, Recent advances in wearable aqueous metal-air batteries:
flexible and rechargeable zinc air batteries, Electrochim. Acta 448 (2023) from configuration design to materials fabrication, Adv. Mater. Technol. 8 (8)
142195. (2023) 2201762.
[159] M. Kurian, et al., Electrode| electrolyte interface enhancement in quasi-solid-state [187] C.Y. Su, et al., Atomic modulation of FeCo–nitrogen–carbon bifunctional oxygen
zinc–air batteries through an anion conducting polymer electrolyte interlayer by electrodes for rechargeable and flexible all-solid-state zinc–air battery, Adv.
in situ polymerization, J. Mater. Chem. A 11 (27) (2023) 14776–14787. Energy Mater. 7 (13) (2017) 1602420.
[160] T. Xu, et al., Seaweed Structure” design for solid gel electrolyte with hydroxide [188] M. Jiao, et al., Recycling spent LiNi1-x-yMnxCoyO2 cathodes to bifunctional
ion conductivity enabling flexible zinc air batteries, J. Colloid Interface Sci. 675 NiMnCo catalysts for zinc-air batteries, Proc. Natl. Acad. Sci. 119 (20) (2022)
(2024) 883–892. e2202202119.
[161] X. Dong, et al., Double-skeleton interpenetrating network-structured alkaline [189] Z. Song, et al., A rechargeable Zn–air battery with high energy efficiency and long
solid-state electrolyte enables flexible zinc-air batteries with enhanced power life enabled by a highly water-retentive gel electrolyte with reaction modifier,
density and long-term cycle life, J. Colloid Interface Sci. (2024). Adv. Mater. 32 (22) (2020) 1908127.
[162] Y. Zuo, et al., Zinc dendrite growth and inhibition strategies, Mater. Today Energy [190] X. Fan, et al., Functionalized nanocomposite gel polymer electrolyte with strong
20 (2021) 100692. alkaline-tolerance and high zinc anode stability for ultralong-life flexible zinc–air
[163] A. Mitha, et al., Surface adsorption of polyethylene glycol to suppress dendrite batteries, Adv. Mater. 35 (7) (2023) 2209290.
formation on zinc anodes in rechargeable aqueous batteries, ChemElectroChem 5 [191] P. Zhang, et al., A flexible zinc-air battery using fiber absorbed electrolyte,
(17) (2018) 2409–2418. J. Power Sources 531 (2022) 231342.
[164] M. Xu, et al., Study of the mechanism for electrodeposition of dendrite-free zinc in [192] G. Liu, et al., All-printed 3D solid-state rechargeable zinc-air microbatteries, ACS
an alkaline electrolyte modified with 1-ethyl-3-methylimidazolium dicyanamide, Appl. Mater. Interfaces 15 (10) (2023) 13073–13085.
J. Power Sources 274 (2015) 1249–1253. [193] W. Fang, et al., Pollen-derived porous carbon decorated with cobalt/iron sulfide
[165] Y. Cheng, et al., Performance and potential problems of high power density hybrids as cathode catalysts for flexible all-solid-state rechargeable Zn–air
zinc–nickel single flow batteries, RSC Adv. 5 (3) (2015) 1772–1776. batteries, Nanoscale 12 (21) (2020) 11746–11758.
[166] W. Lu, et al., Inhibition of zinc dendrite growth in zinc-based batteries,
ChemSusChem 11 (23) (2018) 3996–4006.
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Catalysis Today 445 (2025) 115108

Contents lists available at ScienceDirect

Chemistry in rechargeable zinc-air battery: A mechanistic overview

1. Introduction portable electronic devices. Electric vehicles (EVs) represent a signifi

existing commercial lithium-ion batteries[9,10].

The working principle of a rechargeable zinc-air battery is quite

1.2.4. Electrochemical impedance spectroscopy MOH + OH → MO + H2O + e

1 MS-CoSA-N- 0.76 350 160 mW⋅cm–2 [113]

1 PAM/CS-BT-KBr 110.5mScm− 1 _ 153 mW cm− 2 150 h at 2mAcm− 2 [153]

You might also like

1-s2.0-S0920586124006023-main

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1-s2.0-S0920586124006023-main

Uploaded by

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Share this document

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Did you find this document useful?

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1-s2.0-S0920586124006023-main

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Catalysis Today 445 (2025) 115108

Contents lists available at ScienceDirect

Chemistry in rechargeable zinc-air battery: A mechanistic overview

1. Introduction portable electronic devices. Electric vehicles (EVs) represent a signifi­

existing commercial lithium-ion batteries[9,10].

The working principle of a rechargeable zinc-air battery is quite

1.2.4. Electrochemical impedance spectroscopy MOH + OH → MO + H2O + e

1 MS-CoSA-N- 0.76 350 160 mW⋅cm–2 [113]

1 PAM/CS-BT-KBr 110.5mScm− 1 _ 153 mW cm− 2 150 h at 2mAcm− 2 [153]

You might also like

1. Introduction portable electronic devices. Electric vehicles (EVs) represent a signifi