Applied Energy 128 (2014) 315–324

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Technologies for extending zinc–air battery’s cyclelife: A review

Pucheng Pei ⇑, Keliang Wang, Ze Ma
State Key Lab. of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China

h i g h l i g h t s

 Outlined technological solutions for zinc–air battery’s cyclelife.

 Summarized the latest development of zinc–air battery.
 Analyzed failure of zinc electrode, air electrode.
 Concluded materials, structure, and physicochemical characteristics.

a r t i c l e i n f o a b s t r a c t

Article history: Zinc–air batteries are devices which convert chemical energy into electrical energy and vice versa during
Received 18 February 2014 charge/discharge. Zinc–air battery has been used for a long time due to its high energy density, great
Received in revised form 24 April 2014 availability and low-level pollution, and zinc–air primary battery has already commercialized in hearing
Accepted 27 April 2014
aids, navigation lights, and railway signals so forth; while the problem of cyclelife limits rechargeable
Available online 20 May 2014
zinc–air battery applied to the fields of transportation and energy storage. To thoroughly understand
the nature of electrically rechargeable zinc–air battery, we have made detailed failure mechanism inves-
Keywords:
tigations of zinc electrode, air electrode, electrolyte, and separator; meanwhile research progress of a
Zinc–air batteries
Air electrode
rechargeable zinc–air battery respectively based on bifunctional air electrode and triple electrodes
Zinc electrode described in this work have been analyzed in comparison. Furthermore, working conditions including
Cyclelife air system, electrolyte system and charge–discharge modes influencing zinc–air battery’s cyclelife have
Influence factors been discussed as well. The corresponding solutions are also provided for extending cyclelife of the bat-
Solutions tery, such as horizontal configuration, flowing electrolyte, pulsating currents, corrosion inhibitors, triple
electrodes and so on. These causes and measures will help improve the cyclelife and performance of zinc–
air batteries, and thus offer an alternative to energy storage and transportation.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
2. Failure analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
2.1. Zinc electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
2.2. Air electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
2.3. Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
2.4. Separator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
3. Cyclife discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
3.1. Bi-electrodes mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
3.2. Tri-electrodes mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
3.3. Simulation study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
3.4. Working conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
3.5. Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
4. Progress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322

⇑ Corresponding author. Tel./fax: +86 10 62788558.

E-mail address: pchpei@mail.tsinghua.edu.cn (P. Pei).

http://dx.doi.org/10.1016/j.apenergy.2014.04.095
0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
316 P. Pei et al. / Applied Energy 128 (2014) 315–324

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323

1. Introduction The electrochemical reactions that occur in zinc–air secondary bat-

teries with alkaline electrolyte are as follows:
Zinc–air batteries as a candidate for energy storage may be used
to solve instability of wind power, solar power and the periodical (1) Discharge
peak-trough fluctuation of electrical grid [1,2], which can help to Negative electrode: Zn + 4OH ? Zn(OH)24 + 2e
enhance energy efficiency and optimize loading distribution of Zn(OH)24 ? ZnO + H2O + 2OH
the electrical grid [3,4]. Positive electrode: 1/2O2 + H2O + 2e ? 2OH
As compared to lead acid batteries, flow redox cell, sodium–sul- Overall reaction: 2Zn + O2 ? 2ZnO
phur batteries, lithium ion batteries [5], zinc–air batteries have (2) Charge
high specific energy, low cost, non-pollution and good safety [6]. Cathode: ZnO + H2O + 2OH ? Zn(OH)24
Zinc–air batteries possess cost, safety and technology advantages Zn(OH)24 + 2e ? Zn + 4OH
over lithium–air batteries, aluminum–air batteries, and magne- Anode: 2OH ? 1/2O2 + H2O + 2e
sium–air batteries, and thus it is one of the most promising candi- Overall reaction: 2ZnO ? 2Zn + O2
dates for energy storage [7–9]. The theoretical specific energy of Here we analyze the failure causes of zinc–air battery’s compo-
zinc–air battery is 1350 W h kg 1, but its practical specific energy nents, discuss zinc–air battery based on bifunctional air electrode
is only about 200 W h kg 1 [10]. Currently, zinc–air batteries are and triple electrodes, list the latest progress in the field of zinc–
only applied to the fields of hearing aids, navigation lights, and rail- air rechargeable batteries, and generalize solutions to increasing
way signals. In terms of power and energy storage mainly because cyclelife of zinc–air battery. Lastly, we also put forward the future
of its cyclelife, are still under research and development [11]. To development directions of zinc–air secondary battery research.
meet the requirements of energy storage, the problem of zinc–air
secondary battery’s cyclelife must be resolved. Zinc–air battery’s
2. Failure analysis
cyclelife is mainly related to the dendritic growth of zinc electrode-
postion, morphology shape change of zinc electrode, and the air
2.1. Zinc electrode
electrode failure. Firstly, the formation of dendrites is mostly
dependent on critical overpotential at the tip of dendrites [12]. In
Zinc has a variety of advantages for zinc–air batteries in terms
addition, zincate concentration, electrolyte concentration, temper-
of low equilibrium potential, electrochemical reversibility, high
ature, viscosity and velocity of aqueous solution [13] are also
specific energy, easy availability, low cost, low toxicity, and ease
limiting factors of dendritic growth. There are some effective mea-
of handling [6]. The zinc electrode, which consists of planar elec-
sures to hinder the dendritic growth including current pulses [14]
trode, unconsolidated powder electrode, and consolidated porous
and hydrodynamic conditions [15]. Secondly, two models of the
electrode based on design and structure (see Fig. 1), is most effec-
zinc electrode shape change mechanisms, the concentration cell
tive with large surface area, low self-discharge, and high
model [16] and the electrolyte flow model [17] have been estab-
conductivity.
lished. Adding zinc oxide or calcium hydroxide to the electrolyte,
The typical zinc electrode may be prepared as a mixture of zinc
or controlling convective flow [18] may alleviate the shape change
and zinc oxide particles [26], plus a small quantity of polymeric
to some extent. Thirdly, when the air electrode undergoes hun-
binder and metal oxide additives in porous structure [27]. Com-
dreds of charge–discharge cycles, a variety of unexpected results
pared to zinc planar electrode, a porous electrode largely improves
[19] including catalyst loss, carbon corrosion, blockage and leakage
discharge capacity due to the high effective surface area and elec-
can occur at high charge/discharge current densities. Utilizing tri-
trolyte reservoir [28]. The porosity of zinc electrode is about 60–
electrode structure [20] can be a good alternative to extending
80%, which means the theoretical capacity of zinc active material
the battery’s cyclelife as well as improving the air electrode
in the electrode is approximately 1.2–2.2 A h cm 3 [29,25]. In order
performance.
to improve discharge performance at large currents, smaller parti-
Zinc–air secondary batteries mainly consist of a zinc electrode,
cles have been preferred. However, reducing particle size will lead
an electrolyte and an air electrode, which can be subclassified into
to more severe corrosion due to higher specific surface area in con-
electrically rechargeable zinc–air battery and mechanically
tact with the electrolyte. The porous zinc electrode can be fabri-
rechargeable zinc–air battery [21,22]. Mechanically rechargeable
cated with various morphologies with powder, dendrite, granule,
zinc–air batteries are recharged by zinc electrode and electrolyte
or filament. Dendritic structure with high surface area is suitable
replacement. The zinc electrode is regenerated outside the cell
for high power system. In addition, acetylene black or black carbon
from zinc discharge products withdrawn from the battery. The
is added in the porous zinc electrode [30], to improve the utiliza-
electrically rechargeable zinc–air batteries are recharged inside
tion of zinc active material. Adding cellulose to the pasted zinc
the cell by the bifunctional air electrode or the third electrode.
electrode can improve the conductivity, stability and wettability

Fig. 1. Zinc electrode morphology: (a) planar [23], (b) powder [24], and (c) fiber [25].
 P. Pei et al. / Applied Energy 128 (2014) 315–324
Fig. 2. Zinc deposition morphology [47,48]: (a) mossy, (b) boulder-like, and (c) dendritic.
of zinc electrode [31], thus enhancing cyclelife and peak power
capability of the zinc–air battery [32]. The dissolution current is
associated with the power of zinc–air battery, passivation is with
capacity, corrosion is with charge retention and utilization effi-
ciency, and regeneration is with stability of electrode shape and
morphology [29].
The decreasing discharge capacity of the porous zinc electrode
is closely linked to passivation, electrolyte depletion, porosity
reduction, and conductivity loss. Precipitation followed by zinc
oxidation, dissolution and diffusion in the electrolyte during dis-
charge easily brings about passivation [33,34]. Passivation can be
reduced by the flow rate of electrolyte and the presence of certain
ionic species in the electrolyte, particularly SiO23 and Li+ [35]. Zinc
oxidation reaction accompanied by hydrogen evolution reaction on
the electrode surface will have a negative effect on zinc, electrolyte
and sealing structure [36]. To address the problem of zinc corro-
sion, one is to mix zinc with inorganic elements to increase hydro-
gen evolution overpotential [37,38]; the other is to add a few
organic compounds to the electrolyte to inhibit hydrogen evolution
[39–42].
As for zinc–air secondary battery, the zinc electrode must main-
tain stable over many hundred and even thousand charge/dis-
charge cycles. Morphology is determined by a series of complex
effects of reaction kinetics, diffusion, atomic bond of crystal, nucle-
ation and growth of crystals. Morphological changes of zinc elec-
trodeposition including shape change, dendrites and densification
(Fig. 2) will cause capacity reduction and the battery failure. The
non-uniform current density distribution [43,44] and concentra-
tion gradients in the electrolyte [18] may lead to shape change,
namely the uneven redistribution of zinc active material on the
electrode surface. Densification due to convective electrolyte flows,
which will result in decrease of porosity and active surface area
during cycling, and thereby reduction of zinc electrode kinetics;
while growth of dendrites can cause short-circuit of the battery
because of diffusion-controlled deposition. Zinc deposition mor-
phology is closely related to concentrations of zincate ions,
hydroxide ions, non-uniform current density distributions [45],
Fig. 3. (a) Schematic cross-sectional view of the air electrode, (b) air side morphology, and (c) catalytic side morphology.
317
where concentration gradients negatively affect the morphology.
The deposition morphology tends to be mossy or spongy at low
current densities, layer-like at middle current densities, and boul-
der or dendritic at high current densities. Layer-like morphology is
induced by epitaxial growth of crystal structure and orientation.
Boulder-like morphology can be taken for isoprobability growth
at different crystal faces and orientations. Dendritic growth has
the preferred crystal orientation and crystal face under diffusion
control, while spongy-like deposition is generated by activation
control. Substrate surface conditions only affect early stage of den-
dritic growth. Moreover, adding metal impurities to the electrolyte
such as nickel, indium [38], tetrabutylammonium bromide may
limit dendrites formation, and fluorinated surfactants could sup-
press mossy zinc deposition [46].
2.2. Air electrode
The air electrode is composed of a porous hydrophobic mem-
brane, a catalytic layer and a current collector, as shown in Fig. 3,
which is breathable, leak-proof and conductive, while remaining
active, and stable at high charge–discharge current densities. Air
electrode only participates in oxygen reduction reaction (ORR)
suitable for tri-electrode zinc–air battery; while bifunctional air
electrode may be provided with oxygen reduction reaction and
oxygen evolution reaction (OER).
The power density of zinc–air battery mainly depends on the
performance of the air electrode, namely the rate of oxygen reduc-
tion reaction. Generally, the high rate of oxygen reduction reaction
is reached when approaching the triple-phase interface (electro-
lyte, catalysts, and oxygen) during discharge. This means that elec-
trolyte and oxygen must have access to reaction zone, thus
avoiding channel clog by air electrode flooding or carbonate. The
flooding of the air electrode is caused by the slow penetration of
electrolyte into the gas diffusion layer. The diffusion resistance of
oxygen is thus increased, resulting in a reduced rate for the oxygen
reduction reaction. In order to investigate the failure mode of the
air electrode, X-ray tomography can be used to monitor the flood-
318 P. Pei et al. / Applied Energy 128 (2014) 315–324
ing level in the air electrode [49]. Adding hydrophobic material
such as polytetrafluoroethylene to the air electrode may be an
effective method to solve the problem of air electrode flooding
[50,51].
Above all, the air electrode is needed to suppress corrosion of
the electrode and dissolution of the catalyst at high current densi-
ties during charge, meanwhile the catalytic layer must have high
reaction rates and high stability. Furthermore, hydroxyl ions are
oxidized, forming oxygen which leads to local pressure buildup
within the air electrode, and in turn mechanical degradation of
the air electrode [52]. In addition, carbon dioxide will react with
the alkaline solution leading to pore plugging within the air elec-
trode [53].
2.3. Electrolyte
The electrolyte plays a role as a medium for ionic migration
during discharge/charge, the conductivity of which is a crucial
factor influencing ohmic resistance of the battery. Interest in the
electrolyte mainly focuses on aqueous alkaline solution, gel elec-
trolyte and ionic liquids.
The ionic conductivity of potassium hydroxide is higher than
that of sodium hydroxide under the same conditions [54], which
increases along with alkaline concentration to some extent. How-
ever, the increase of solution concentration also leads to its high
viscosity, thus decreases the transfer rate of hydroxyl ions [55].
Temperature and humidity affect the performance of the battery,
wherein high temperatures could cause water to evaporate. This
increase the electrolyte concentration and the transfer resistance
of hydroxyl ions, but can improve ionic conductivity [56]. Zinc–
air batteries may display good performance at high temperatures,
but adverse effects may be produced by high temperatures. Zinc
corrosion is generated at the low temperatures, and the perfor-
mance of zinc–air batteries deteriorates under the condition of var-
iable operating conditions [57]. Discharge product is also related to
the concentration of electrolyte, where the main reaction product
is Zn(OH)24 in high concentration alkaline solution during dis-
charge, whereas precipitation in low concentration alkaline solu-
tion is Zn(OH)2 crystal [58]. However, there are many problems
in the conventional zinc–air battery with aqueous electrolyte such
as water electrolysis, carbonate formation and drying-out of the
battery.
To solve the electrolyte leakage, gel electrolytes have also been
shown to serve as a species transport medium in zinc–air battery.
Mohamad [59,60] demonstrated that potassium hydroxide solu-
tion mixed with hydroponics gel can be employed as a new alka-
line electrolyte for zinc–air batteries. Yang and Lin [61] provided
an alkaline composite PEO–PVA–glass–fiber–mat polymer electro-
lyte which can be applied to solid-state primary zinc–air batteries
due to the ionic conductivity of 10 2 S cm 1. In addition, adding gel
to the electrolyte can increase viscosity to make zinc powder sus-
pended in the electrolyte, and thereby control the porosity of the
zinc electrodes.
Ionic liquids may be a promising alternative to the electrolyte
due to non-flammability, high thermal stability and low volatility
[62–64]. Kar et al. [65] studied ionic liquids based on quaternary
alkoxy alkyl ammonium cations and confirmed that they can act
as coordinating ligands in the deposition of zinc ion. Simons
et al. [66] investigated the deposit morphology of 10 mol% Zn(dca)2
in 1-ethyl-3-methylimidazolium dicyanamide [emim] [dca] ionic
liquid with 3 wt% of water glassy carbon, obtaining uniform depos-
its of zinc metal and 45 mA cm 2 of high current densities. D. R.
MacFarlane et al. [67] comprehensively analyzed ionic liquids
related to energy applications. As compared to potassium hydrox-
ide, lower ion conductivity of ionic liquids is still a challenging
problem, and considerable work still need to be done.
2.4. Separator
The main function of a separator in a zinc–air battery is to pre-
vent mixing of the positive and negative electrolytes but to selec-
tively allow the ions to migrate [68]. The separator can retard zinc
dendrites growth to some extent, and simultaneously meet the
basic requirements including stability, electrical insulation, ionic
conductivity and electrolyte storage [69]. Based on the above
requirements, organic polymer porous membranes can be com-
monly used as the separator in a zinc–air battery [55], such poly-
propylene as Celgard 4560 and Celgard 5550 [70]. In addition, an
inorganic MCM-41membrane [71] was made from cationic surfac-
tant, cetyltrimethyl-ammonium bromide, and the silica-covered
organic template, which can improve the capacity of the battery.
To effectively prevent zinc cation permeation from the anode to
the cathode, polysulfonium membranes can be an effective alter-
native material to be used as the separator of zinc–air batteries
[70,72,73].
3. Cyclife discussion
Zinc–air batteries need to be recharged using different currents
or voltages when battery voltage is below the preset value, but the
charging voltage must be higher than the discharging voltage due
to polarization. In general, the cyclelife of a rechargeable zinc–air
battery indicates how many times it can completely undergo the
charge–discharge process until failure. The charge process will
end if the battery capacity is fully charged, and the discharge pro-
cess will continue until the battery voltage drops to cut-off voltage.
Bi-electrodes or tri-electrodes may be used for regeneration of
zinc–air batteries, where bi-electrodes are structurally compact
but has limited life, high cost, and technological problems, while
triple electrodes have a long life but are structurally complex.
3.1. Bi-electrodes mode
Electrochemical charge–discharge functions of zinc–air batter-
ies can be realized by bi-electrodes, as shown in Fig. 4, mainly
depending on bifunctional air electrode. The oxygen reduction
reaction occurs at the triple-phase interface, whereas the oxygen
evolution reaction (OER) occurs at the two-phase interface.
Bifunctional air electrode can be divided into two categories
[74]. One uses a single catalytic layer for ORR and OER, such as
La2O3 [75], Co3O4 [76], LiMn2 xMxO4 [M = Co, Fe,(CoFe)] [77], La0.6-
Ca0.4CoO3 [78–81], La0.6Ca0.4MnO3 [82], and LaNiO3 [83], where the
manufacture and assembly of this construction is relatively simple
but requires highly stable catalyst materials to withstand the
intense redox conditions. The other is to employ multiple catalytic
layers with different porosity and hydrophobicity [84], wherein the
hydrophilic side used for OER is facing the electrolyte, the part for
ORR oriented towards the air side, and a current collector placed
between the two functional layers. This electrode might offer bet-
ter performance but manufacturing complexity and increasing
mass transfer loss.
Burchardt and Becquet tested several catalysts for metal–air
battery [52], where the battery with a combination of La2O3 and
MnSO4, La2O3 and MnO2, Ag and MnSO4, Ag and La2O3 as catalysts
exhibited 150 cycles, 95 cycles, 50 cycles at discharge/charge rates
of 100 mA cm 2. Kubo et al. [85] found that the air electrode with
Ni–Fe–CO23 -layered double hydroxide (NiFe CO23 LDH) can
improve catalytic activity. Furthermore, NiFe CO23 LDH would
keep stable in air due to a limited influence of carbon dioxide.
Nitrogen-doped carbon nanotubes (NCNT) as the catalyst of
ORR can improve the electrical conductivity of the air electrode
as a consequence of the four electron transfer reaction pathway
 P. Pei et al. / Applied Energy 128 (2014) 315–324
Fig. 4. Schematic view of zinc–air battery based on bi-electrodes.
[86–92]. However, when compared to relatively stable MnO2
behavior, NCNT showed poor OER performance. The MnO2–NCNT
composite displayed superior electrical and electrochemical
performance when compared to the pure MnO2 in terms of
charge/discharge current densities and impedance (Fig. 5) [93].
Chen et al. [94] proposed a new class of core-corona structured
bifunctional catalyst (CCBC-2) from NCNT and LaNiO3, where
LaNiO3 was worked as the core structure for OER catalyst, and
NCNT was served as the corona component for ORR catalyst, as
shown in Fig. 6(a). The results demonstrated that zinc–air batteries
with CCBC-2 had excellent activity and stability compared with
single Pt/C and LaNiO3 during discharge/charge (Fig. 6(b)) [95].
Fig. 5. (a) MnO2 nanotube, (b) NCNT, (c) discharge/charge polarization curves of the battery with MnO2 and MnO2–NCNT, and (d) nyquist plot of MnO2 and MnO2–NCNT [93].
319
Li et al. developed advanced rechargeable zinc–air batteries
with novel catalyst CoO/NCNT hybrid oxygen reduction catalyst
and Ni–Fe-layered double hydroxide (NiFe LDH)/CNT oxygen evo-
lution catalyst for the cathode [20,96], as shown in Fig. 7. In the
electrolyte of 6 M KOH and 0.2 M zinc acetate, the battery displays
cycling stability and short cycle times (200–2000 s) at low current
densities of 5–10 mA cm 2, while the battery exhibits long cycling
times (20 h) at high current densities of 20 mA cm 2, causing oxi-
dation and loss of CoO/NCNT, thus deteriorated battery
performance.
Pan et al. [97] developed a new type of flow zinc–air battery
with nano-structured Ni(OH)2 and MnO2–NaBiO3 as bifunctional
catalysts (Fig. 8). The battery displayed a discharge voltage of
1.32 V with an average coulombic efficiency of 97.4% and an energy
efficiency of 72.2% in 150 cycles.
In light of the above mentioned catalyst material, mixing nickel-
based OER catalyst and manganese, or cobalt-based ORR catalyst as
the bifunctional catalysts of air electrode, can be regarded as a
practical method. However, zinc–air batteries with this structure
need take the following problems into consideration. Firstly, the
cost of developing appropriate catalysts will be high. Secondly,
oxygen bubbles released by charging will impact catalysts of the
air electrode, resulting in catalysts loss. Thirdly, the air electrode
corrosion will occur at high current densities during charging,
shortening the battery’s cyclelife. Thus, the bifunctional air elec-
trodes will have low rates for the oxygen evolution reaction
(<50 mA cm 2).
3.2. Tri-electrodes mode
Zinc–air batteries may also realize charge and discharge modes
by means of triple electrodes, which can improve the cyclelife and
energy efficiency of the battery, mainly because the charging pro-
cess does not use the air electrode. Third electrode and air elec-
trode may be located on either side of zinc electrode (in Fig. 9)
320 P. Pei et al. / Applied Energy 128 (2014) 315–324

Fig. 6. (a) CCBC-2 model, (b) discharge/charge polarization curves of Pt/C, CCBC-2, and LaNiO3 [94].

Fig. 7. (a) Model and morphology of CoO/NCNT, (b) model and morphology of NiFe LDH/CNT, and (c) performance of the battery [20].

Fig. 8. (a) Schematic view of the flow zinc–air battery, and (b) coulombic efficiency and energy efficiency in 150 cycles [97].

where the structure is complex but beneficial to the air electrode;
or zinc electrode and the air electrode may be located on the two
sides of the third electrode where the structure is compacted but
easily causes gas bubbles to accumulate, producing shape change
of the air electrode, then resulting in battery leakage. In general,
nickel or nickel alloy may be employed as the third electrode of
the alkaline zinc–air battery which is related to electrolyte
characteristics.
The activity of the air electrode mainly depends on active char-
acteristics of catalysts, wherein the oxygen reduction catalyst may
be selected from MnO2 [98–100], MnSO4, Co, Fe, Ag [57,101], Pt
and Pd. The stability of metal-based catalysts in the electrolyte
decreases in the following order: Pt > Ag > Pd > Co > Fe > Mn.
MnO2 as the oxygen reduction catalyst has a cost advantage and
good stability, high oxygen reduction reaction activity in alkaline
electrolyte as a result of the two-electron ORR pathway. It may
yield HO2 during ORR, resulting in shifting to a more negative
value and corrosion of the electrode material. MnO2 will be
reduced to MnOOH and Mn3O4 under anaerobic conditions, in
which hydrogen peroxide ions further reduce hydroxyl ions,
improving the performance of the gas diffusion electrode
[102,103]. Although Ag- or Pt-based catalyst has good ORR activity,
 P. Pei et al. / Applied Energy 128 (2014) 315–324
Fig. 9. Schematic view of zinc–air battery based on tri-electrodes.
these catalysts are expensive. Fe-based catalysts present excellent
ORR activity but poor stability, which is the opposite of Co-based
catalysts. One approach is a mixture of higher stability and activity
of catalysts to play their advantages, respectively [104]. Another is
metal-based precursors combined with carbon nanotube [20] or
nitrogen-doped grapheme [105].
Li et al. [20] explored rechargeable zinc–air batteries with a tri-
electrode configuration, wherein CoO/N-CNT and Ni–Fe LDH/CNT
respectively served as the catalysts of ORR and OER. The battery
exhibited similar current densities as the rechargeable battery
made with Pt/C and Ir/C for the catalysts of ORR and OER, respec-
tively. The battery showed charge/discharge polarization of 0.70 V,
4–20 h long charge/discharge cycles at 20–50 mA cm 2. Toussaint
et al. [19] found that using a nickel electrode as charging electrode
in zinc–air batteries may help to shorten charge/discharge cycles,
and improve the power and energy efficiency of the zinc–air bat-
teries. Stacburski [106] designed a structure that can rotate zinc
electrode to prevent zinc dendrite growth during charge, and dis-
charge product can be suspended within the electrolyte to effec-
tively solve zinc electrode passivation.
Amendola et al. devised rechargeable zinc–air batteries
arranged in a horizontal orientation [107], as shown in Fig. 10.
An air electrode and a zinc electrode were provided as a top layer
and a bottom layer of a cell, respectively. The electrolyte was con-
tained by the frame, the zinc electrode, and the air electrode. There
may be no need for a separating membrane between the zinc elec-
trode and the air electrode due to gravity separating materials of
different densities. An airflow tunnel was provided between the
zinc electrode of the first cell and an air electrode of the second
cell. This horizontal configuration together with gravity can help
the precipitated discharge product to settle as an even layer on a
zinc electrode. Amendola et al. developed a type of zinc–air battery
that would be suitable to store large quantities of energy at a low
cost for 2700 cycles without the performance degradation.
It can be found that tri-electrode structure has some advantages
over bifunctional air electrode. Firstly, it can reduce the catalysts
Fig. 10. Profile and structure of rechargeable zinc–air batteries arranged in a horizontal orientation.
321
loss and carbon corrosion of air electrode. Secondly, it can still be
fit for current pulses to limit dendritic growth, and thus extend
the battery’s cyclelife. Moreover, the tri-electrode structure can
also lessen the air electrode polarization. However, the tri-elec-
trode structure is relatively complicated.
3.3. Simulation study
In order to delve deeply into electrode kinetics, and cycling
parameters of zinc–air battery, it is necessary to use simulation
techniques in contrast with testing methods, such as cyclic voltam-
metry, scanning electron microscopy, impedance spectroscopy and
so on.
Deiss et al. [108] developed a one-dimensional numerical
model of electrically rechargeable alkaline zinc–air battery to opti-
mize the battery structure, including species diffusion, migration,
chemical and electrochemical reactions in the porous zinc elec-
trode and on the surface of air electrode. Song et al. [109] estab-
lished a one-dimensional mathematical model of zinc electrode
to simulate the discharge process under high current density con-
ditions which can analyze failure mechanisms of zinc electrode.
Matsushita et al. [110] simulated fractal structures of zinc electro-
deposition on the basis of a diffusion-limited-aggregation model.
Although some simulation methods have been conducted from
the above, numerical analysis should be strengthened to keep up
with testing progress, especially the lack of three-dimensional sim-
ulation of zinc–air battery.
3.4. Working conditions
The battery charge/discharge mode, electrolyte system and air
management system will affect the performance and cyclelife of
zinc–air battery as well as the design, manufacture, and assembly
of battery to some extent.
Compared to the static electrolyte, the flowing electrolyte can
take away discharge product in time, unaffecting the subsequent
reaction rate during discharge; the flowing electrolyte can also
help to prevent the growth of zinc dendrites and formation of
the even layer of zinc deposition during charge [15]. In addition,
the flowing electrolyte may intimately take away heat and gas
bubbles generated by the electrochemical reaction process, and
help to manage the battery thermal system. However, if the flow-
ing velocity of electrolyte is too high, it will be necessary to scour
the catalytic layer of air electrode and surface morphology of zinc
electrode.
Furthermore, pulsating current can be generally used for zinc
electrodeposition to obtain fine-grain deposits. Shaigan et al. [14]
investigated the effect of pulse current parameters including duty
cycle and frequency on the deposit morphology in 4, 6 and 9 M
KOH electrolytes contained dissolved zinc oxide. The results
showed that mossy deposits occurred at low direct current densi-
ties, and dendrites grew at high direct densities. Reducing the duty
cycle and increasing the frequency resulted in finer grain deposits
for 4 and 6 M KOH, but pulse deposition did not improve the
dendrites morphology in 9 M KOH.
322 P. Pei et al. / Applied Energy 128 (2014) 315–324
Table 1
Rechargeable zinc–air battery technology status.
Organization Feature
EOS Tri-electrode, horizontal structure, neutral
electrolyte
Fluidic energy Ionic liquids
Stanford University OER & ORR catalysts: CoO/NCNT, NiFe LDH/
CN
Revolt Technology Bifunctional catalysts, alkaline electrolyte
EDF, France Bicatalysts: MnO2/NiCo Zn/TiN/a polymer
binder, 7 M KOH
University of Waterloo Bifunctional catalysts: Co3O4 nanowire/
stainless steel
National University of Singapore MnO2/Ag catalysts, 6 M KOH, zinc plate
Daegu Gyeongbuk Institute of Science Bifunctional catalysts: CoMn2O4/N-rGO
and Technology
Zinc–air batteries employ oxygen from ambient air as a reactant
during discharge, while oxygen is discharged to the atmosphere
through the air permeable electrode during charge, so zinc–air
battery is an open system. Carbon dioxide, ambient humidity will
affect the battery’s cyclelife. Therein carbon dioxide will react with
alkaline electrolyte to produce carbonate blocking the air path-
ways of the air electrode. Amine-based absorbents [111] or solid
adsorbents [53,112] including Ca(OH)2, LiOH, and soda-lime are
required to remove carbon dioxide from the atmosphere. If ambi-
ent humidity is greater than equilibrium relative humidity value
in zinc–air battery, zinc–air battery will absorb water from the
air through the cathode leading to air electrode flooding. If the
ambient humidity is less than the equilibrium relative humidity
value, the zinc–air battery will release water vapor from the elec-
trolyte through the air cathode, and will then dry out [113], a result
which may also arise from other reasons such as leakage or high
temperature. There are two approaches to improving operating
conditions of zinc–air batteries [114]. One is to control the electro-
lyte concentration ensuring the partial pressure of water inside the
zinc–air batteries is in equilibrium with the ambient water vapor
pressure. The other is to optimally design the structure of the bat-
tery, and thus control electrolyte volumes.
Once the structure of battery might be determined, working
conditions have a great impact on the battery’s performance as
well. Charge/discharge modes, air physical state and physiochem-
ical characteristics of electrolyte can also affect zinc–air battery’s
cyclelife.
3.5. Solutions
In view of the aforementioned analysis, the main influencing
factors and solutions to the zinc–air battery’s cyclelife are outlined
as follows:
(1) Zinc-dendrite growth: where the flowing electrolyte, charg-
ing mode such as pulsating current and current densities,
properties of electrolyte, special separator material and hor-
izontal orientation configuration can effectively limit den-
dritic growth of zinc deposition during charge.
(2) Zinc electrode failure: owing to densification and shape
change, where shape change can be addressed by optimiza-
tion of zinc electrode structure, the flowing electrolyte, and
adding calcium hydroxide or zinc oxide to the electrolyte.
Densification can be solved by means of charging currents.
Besides, zinc corrosion may be suppressed by means of
alloying zinc with other higher overpotential metals or add-
ing inhibitors to the electrolyte.
(3) Air electrode degradation including catalysts loss and carbon
corrosion: electrically rechargeable zinc–air batteries with
tri-electrode configuration can improve power and energy
Status of technology References
2700 Cycles at 2.1 V charge voltage, 0.9 V discharge voltage [107]
5000 Cycles [63]
20 h Cycle period, 0.7 V charge–discharge voltage [20]
polarization at 20 mA cm 2
200 Cycles at 100 mA cm 2 [52]
200 Cycles at 15 mA cm 2 [19]
100 Cycles at 50 mA [115]
270 Cycles at charge potential 2.6 V [116]
100 Cycles, 0.86 V charge/discharge polarization at [117]
20 mA cm 2
efficiencies without degradation, combined with hybrid cat-
alyst technology like respectively employed CoO/N-CNT, Ni–
Fe LDH/CNT as ORR and OER catalysts. In addition, carbon
dioxide absorption and humidity control are also crucially
important to extend air electrode life.
(4) Electrolyte aging: some measures such as flowing electrolyte
or ionic liquid may be taken to address problems of carbon-
ate and concentration change.
Last but not the least, zinc–air battery’s cyclelife is affected by
the discharge rate and depth of discharge, and by other conditions
such as temperature and humidity.
4. Progress
To overcome the above-mentioned constraints affecting batter-
ies performance and cyclelife, researchers around the world have
carried out ongoing experimental studies. Some progress in the
zinc–air battery has been made in recent years, as shown in
Table 1.
Table 1 displays that the material field of catalyst and electro-
lyte should receive much more attention. Zinc–air batteries as
the basis of bifunctional catalysts are suitable for small power
requirements due to their low discharge rate, while zinc–air bat-
tery based on tri-electrode structure and ionic liquid can be
applied to energy storage because of their high discharge rate,
and a long cyclelife. In consequence, it is required to weigh over
the performance and cyclelife of the zinc–air battery according to
different applications.
5. Conclusion
Zinc–air batteries are suitable for energy storage due to several
advantages: namely high energy density, abundance, safety and
environmental compatibility. However, the main challenge of the
zinc–air rechargeable battery is to extend cyclelife. The cyclelife
of the zinc–air battery would be constrained by morphological
changes of zinc electrode and air electrode failure. The mechanism
for morphological evolution can be attributed to the diverse reac-
tion rates on zinc electrode surface, non-uniform charge/discharge
current densities, variously gradient forces and uneven deposition
morphology. The air electrode failure may be ascribed to flooding,
catalysts loss, support material corrosion, and carbonate plugging.
To address the problem of the battery’s cyclelife, the key areas of
development must be carried forward.
 P. Pei et al. / Applied Energy 128 (2014) 315–324
 Research and development of catalysts, which will mainly focus
on redox reaction near or at the cathode surface. One is to
develop suitable catalysts for OER and ORR. The other is to
reduce charge/discharge polarization, and to increase the cycle
efficiency.
 Research of zinc electrode, where the porosity stability of the
porous electrode in operation and the uniform processing tech-
nology of zinc electrode are still outstanding issues.
 Research of electrolyte, which will receive more attention to
solve problems of the electrolyte leakage, evaporation, and
decomposition. Moreover, it is necessary to develop a new elec-
trolyte guaranteeing the relatively stable characteristics of the
electrolyte during charge/discharge.
 Optimization of battery structure, which can effectively guide
the electrolyte and oxygen flows to improve battery perfor-
mance during charge/discharge.
 Integration of battery management system, where charge–dis-
charge mode can be coupled with air system and electrolyte
system to obtain uniformly morphological changes according
to operating conditions.
Acknowledgements
This work has been funded by National Natural Science Founda-
tion of China (No. 21376138), National Basic Research Program of
China (973 Program) (2012CB215505), and National High Technol-
ogy Research and Development Program of China (863 Programs)
(2012AA1106012, and 2012AA053402).
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