Recent Progress of Metal-Air Batteries-A Mini Review-Aplicatii MAB PDF

applied
sciences
Review
Recent Progress of Metal–Air Batteries—A Mini Review
Chunlian Wang 1 , Yongchao Yu 2 , Jiajia Niu 3 , Yaxuan Liu 2 , Denzel Bridges 2 , Xianqiang Liu 3 ,
Joshi Pooran 4 , Yuefei Zhang 3 and Anming Hu 1,2, *
1 Institute of Laser Engineering, Beijing University of Technology, Beijing 100124, China
2 Department of Mechanical, Aerospace and Biomedical Engineering, University of Tennessee, Knoxville,
TN 37996, USA
3 Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology,
Beijing 100124, China
4 Oak Ridge National Lab, Oak Ridge, TN 37831, USA
* Correspondence: ahu3@utk.edu

Received: 3 June 2019; Accepted: 6 July 2019; Published: 11 July 2019
Featured Application: This paper can provide the basic knowledge on metal-air batteries for
beginners and relevant comprehensive review for researchers.
Abstract: With the ever-increasing demand for power sources of high energy density and stability
for emergent electrical vehicles and portable electronic devices, rechargeable batteries (such as
lithium-ion batteries, fuel batteries, and metal–air batteries) have attracted extensive interests. Among
the emerging battery technologies, metal–air batteries (MABs) are under intense research and
development focus due to their high theoretical energy density and high level of safety. Although
significant progress has been achieved in improving battery performance in the past decade, there are
still numerous technical challenges to overcome for commercialization. Herein, this mini-review
summarizes major issues vital to MABs, including progress on packaging and crucial manufacturing
technologies for cathode, anode, and electrolyte. Future trends and prospects of advanced MABs by
additive manufacturing and nanoengineering are also discussed.
Keywords: metal–air batteries; laser processing; 3D printing
1. Introduction
1.1. Market Demand and Technical Tendencies

With the continued growth of the global economy, the demand for energy has significantly
increased. Unfortunately, Earth’s conventional non-renewable energy resources, such as coal, oil, and
natural gas, are limited. Hence, the development of new energy devices is important for a sustainable
society. Innovative biofuel batteries, supercapacitors, and metal–air batteries are among the most
suitable candidates to meet the energy storage demand [1–6]. Among the various power storage
devices currently on the market, lithium-ion batteries (LIBs) have the best performance. However,
it is still a challenge to achieve high capacity (>200 mA h g−1 ) in LIBs and to meet safe energy storage
requirements for electric vehicles [7,8]. Recently, MABs attracted significant attention as they can
operate in an open-air atmosphere. MABs consist of metal anodes and an air cathode. The MAB
cathode uses oxygen from ambient air, which leads to significant battery weight reduction, which has
unprecedented advantages for many applications. Compared to other batteries, especially Lithium-ion
batteries, which currently dominate the market share, MABs are cheap, because the cathode source
(oxygen from air) is abundant and the anode can be made using low-cost metals, such as, Al, Zn, Fe.
Figure 1 shows the application of MABs as the energy storage system for various technologies. MABs
Appl. Sci. 2019, 9, 2787; doi:10.3390/app9142787 www.mdpi.com/journal/applsci

Appl.Sci.
Appl. Sci.2019,
2019,9,
9,2787
x FOR PEER REVIEW 22of
of22
22
technologies. MABs are attractive not only as compact power sources for portable electronics and
electric
are vehicles
attractive but also
not only as compelling
as compact energy for
power sources transfer stations
portable or energy
electronics storage vehicles
and electric devices but
to manage
also as
energy flow
compelling among
energy renewable
transfer energy
stations generators,
or energy storage such as to
devices wind turbines
manage and
energy photovoltaic
flow panels,
among renewable
electricgenerators,
energy grids and end-users.
such as wind turbines and photovoltaic panels, electric grids and end-users.
Figure 1. Applications
Figure1. Applications of
of metal–air
metal–air batteries
batteries as
as energy
energysource
sourceand
andstorage
storagesystems.
systems.
Theoretical
Theoretical energy
energy density
density isis an
an important
important factor
factor in
in evaluating
evaluating thethe performance
performance of of various
various
battery
battery configurations.
configurations. Figure
Figure 22 shows
shows theoretical
theoretical energy
energy density,
density, specific
specific energy,
energy,and
andnominal
nominal cell
cell
voltage of different metal-air batteries (MABs) [9]. As oxygen, directly supplied from
voltage of different metal-air batteries (MABs) [9]. As oxygen, directly supplied from the surrounding the surrounding
environment,
environment, is is involved
involved in in the
the cathode
cathode as as an
an oxidant
oxidant during
during the
the discharge
discharge period,
period, MABs
MABs show
show
considerably
considerably higher
higher energy
energy density.
density. Although,
Although, theoretically,
theoretically, lithium–air
lithium–air batteries
batteries (LABs)
(LABs) offer
offer the
the
best combination of the highest theoretical energy density (5928 Wh kg −1 ) and high cell potential
best combination of the highest theoretical energy density (5928 Wh kg ) and high cell potential
−1
(nominally
(nominally2.96
2.96 V),
V),iron–air
iron–airbatteries
batteries (FABs)
(FABs)possess
possessthe thesmallest
smallesttheoretical
theoreticalenergy
energydensity
densityand
andcell
cell
voltage
voltage (nominally
(nominally 1.28 1.28 V).
V). Al-,
Al-, Zn-,
Zn-, and
and Fe–air
Fe–air batteries
batteries are
are also
also the
the research
research hotspots
hotspots because
because ofof
economic and safety considerations.
economic and safety considerations.
In
Inthe
the present
present paper,
paper,aluminum–air
aluminum–airbatteries
batteries(AABs),
(AABs),zinc–air
zinc–airbatteries
batteries(ZABs),
(ZABs),iron–air
iron–airbatteries
batteries
(FABs),
(FABs), and lithium–air batteries (LABs) have been reviewed with a focus on working principleand
and lithium–air batteries (LABs) have been reviewed with a focus on working principle and
device
device configuration,
configuration, and and performance
performance progress.
progress. In In addition,
addition, major
major technology
technology barriers
barriers have
have been
been
identified,
identified,and
andpossible
possiblesolutions
solutionsdiscussed.
discussed. Emerging
Emerging advanced
advanced manufacturing
manufacturing methods, suchsuch
methods, as 3Das
printing and laser processing techniques, for the development a high-performance
3D printing and laser processing techniques, for the development a high-performance rechargeable rechargeable MABs,
have
MABs,also been
have discussed.
also been discussed.
1.2.
1.2. Working
Working Principles
Principles
The
The working
working principle
principle of
of MABs
MABsdiffers
differsfrom
fromthat
thatofoftraditional
traditionalionic
ionicbatteries.
batteries. The
Thetraditional
traditional
ionic
ionic batteries involve the transformation of metallic ions from the anode to the cathode. In
batteries involve the transformation of metallic ions from the anode to the cathode. In MABs,
MABs,
metals
metals or alloys transform to metallic ions at anode and oxygen transforms to hydroxide ions at
or alloys transform to metallic ions at anode and oxygen transforms to hydroxide ions atthe
the
cathode. Figure 3 shows the operation of a MAB in aqueous or non-aqueous electrolyte
cathode. Figure 3 shows the operation of a MAB in aqueous or non-aqueous electrolyte medium. In medium.
In
anan aqueous
aqueous electrolytesystem,
electrolyte system,oxygen
oxygendiffuses
diffusesinto
intobatteries
batteriesthrough
through the
the gas
gas diffusion
diffusion layer
layer and
and
transforms
transforms into receiving electrons forming oxygen anions. In a non-aqueous electrolyte system,
into receiving electrons forming oxygen anions. In a non-aqueous electrolyte system,
oxygen
oxygen receives
receives electrons
electrons and
andtransforms
transformsinto
intooxygen
oxygenanion.
anion. Metals
Metals release
release electrons,
electrons, transform
transform toto
Appl. Sci. 2019, 9, 2787 3 of 22
Appl. Sci.
Appl. Sci. 2019,
2019, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 33 of
of 22
22
metallic ions
metallic ions and
and dissolve
dissolve into
into electrolytes.
electrolytes. These
These processes
These processes will
processes will be reversible
will be
be reversible during
reversible during aa charging
charging
procedure of a rechargeable
procedure of a rechargeable MAB.
rechargeable MAB.
MAB.
Figure 2.
Figure 2. Theoretical
Theoretical specific
specific energies,
energies, volumetric
volumetric energy
energy densities,
densities, and
and nominal
nominal battery
battery voltages
voltages of
of
various metal–air
various metal–air batteries
batteries (MABs)
(MABs) [9].
[9].
Figure
Figure 3.
Figure Schematic
3. Schematic
3. diagrams
Schematic diagrams of
diagrams of MABs
of MABs working
MABs working principles
working principles for
principles for (a)
for (a) non-aqueous
(a) non-aqueous electrolyte,
non-aqueous electrolyte, and
electrolyte, and (b)
and (b)
(b)
aqueous
aqueous electrolyte.
electrolyte.
aqueous electrolyte.
For MABs,
For MABs, oxygen
MABs, oxygen and
oxygen and metals
and metals participate
metals participate in
participate in electrochemical reactions.
in electrochemical
electrochemical Specific
reactions. Specific reaction
Specific reaction formulas
reaction formulas
formulas
For reactions.
are as
are as Equations
as Equations (1) and
Equations (1,2):
(1,2): (2):
are
Anode: M
Mn+ + ne− (1)
Anode: M
Anode: M ⇌ ⇌ MMn+n+ + ne--
+ −ne (1)
(1)
Cathode: O2 + 2H2 O + 4e
4OH− (2)
The reaction kinetics of FABsCathode:

Cathode: Oalkaline
in theO + 2H
22 + 2H22O
Oaqueous
++ 4e ⇌ electrolyte
4e−− ⇌ 4OH--
4OH (2)
are shown in Equations(2) (1)
and (6)
The [10].
The reaction
reaction kinetics
kinetics of
of FABs
FABs in
in the
the alkaline
alkaline aqueous
aqueous electrolyte
electrolyte are
are shown
shown in
in Equations
Equations (1)
(1) and
and
− −
(6) [10].
(6) [10]. Anode: Fe + 2OH
Fe(OH) 2 + 2e (3)
− - −
3Fe(OH)2 + Fe
Anode:
Anode: 2OH
-Fe
Fe ++ 2OH
2OH 4 + 4H222 O
- ⇌OFe(OH)
⇌3 Fe(OH) + -2e
++ 2e
2e (3)(4)
(3)
Appl. Sci. 2019, 9, 2787 4 of 22
Cathode: O2 + 2H2 O + 4e−

4OH− (5)
Overall reaction: 2O2 + 3Fe

Fe3 O4 (6)
The working principle of AABs in the alkaline aqueous electrolyte is shown in (9) [11].
Anode: Al + 4OH−
Al(OH)4 − + 3e− (7)

4OH− (8)
Overall reaction: 3O2 + 2Al

Al2 O3 (9)
The working principle of ZABs in the alkaline aqueous electrolyte is shown in (13) [12].
Anode: Zn + 4OH−
Zn(OH)4 2− + 2e (10)
Zn(OH)4 2−
ZnO + 2OH− + H2 O (11)

4OH− (12)
Overall reaction: O2 + Zn
ZnO (13)
The working principle of LABs in the non-aqueous electrolyte is shown in (18) [1].
Anode: Li
Li+ + e− (14)
Cathode: O2 + e−
O2 − (15)
O2 − + Li+
LiO2 (16)
LiO2 + Li+ + e−
Li2 O2 (17)
Overall reaction: O2 + Li
Li2 O2 (18)
1.3. Configuration of MABs

Based on packaging and practical application requirements, MABs can be classified as traditional
static batteries, flow batteries, and novel flexible batteries [13]. In this part, three kinds of batteries will
be discussed briefly. The latter part is based on the analysis of solid-state batteries.
Traditional static batteries: As shown in Figure 3, traditional static air batteries have four main
parts: cathode, separator, electrolyte, and anode. Compared to the fast kinetics of the anode reaction,
oxygen reaction on cathodes is kinetically sluggish in nature. A three-phase reaction boundary of
solid (catalyst)–liquid (electrolyte)–gas (oxygen) contributes to the oxygen reduction reaction (ORR).
Meanwhile, a reversed oxygen evolution reaction (OER) occurs on a two-phase boundary solid
(catalyst)–liquid (electrolyte) at the cathode [14]. Highly efficient bifunctional catalysts are thus
required to facilitate both OER and ORR. In addition, since an active electrolyte is employed in
traditional static MABs, it is challenging to completely overcome the issue of insoluble deposition of
by-products on the surface of both the metal anode and air cathode during the charge–discharge cycles.
These deposited by-products consequently block the electrode pores limiting the diffusion of air that
eventually results in a lower battery performance [15].
Flow batteries: This type of MAB consists of an electrode, separator, electrolyte, and an electrolyte
bank installed as an additional part. Usually, a pump is also integrated to drive electrolyte flow,
as shown in Figure 4b. Flowing-electrolyte configuration addresses some of the problems associated
with the metal anode and an air cathode. For instance, in zinc–nickel batteries, a large volume of
flowing electrolyte decreases the formation of dendrites and irregular shape changes of zinc and
thereby, avoid passivation by improving current distribution and reducing concentration gradients [16].
However, the complicated flowing-configuration of MABs has some shortcomings, including decreased
Appl. Sci. 2019, 9, x FOR PEER REVIEW 5 of 22
Appl. Sci. 2019, 9, 2787 5 of 22
gradients [16]. However, the complicated flowing-configuration of MABs has some shortcomings,
including decreased energy efficiency and volume density, and increased complications as additional
energy efficiency
pumps and tubesand volume to
are needed density,
drive and increased
the flow complications
of electrolyte duringasthe additional
discharge. pumps and tubes are
needed to drive the flow of electrolyte during the discharge.
Flexible batteries: With the increasing demand for portable electronics in recent years, light and
smallFlexible batteries:
form-factor With
flexible the increasing
batteries have becomedemand forresearch
a hot portabletopic
electronics
[17,18].inThe
recent
mainyears, light and
components
small form-factor flexible batteries have become a hot research topic [17,18].
of a flexible battery include a cathode, anode, separator, and high conductivity electrolyte. The main components of a
flexible battery include a cathode, anode, separator, and high conductivity electrolyte.
Conventional electrolyte for a flexible battery system is a solid-state electrolyte. A thin metallic plate Conventional
electrolyte
is used as afor a flexible
metal anodebattery system
to reduce is a solid-state
the battery weight.electrolyte.
Various nano A thin metallic plate
compounds and is used as a metal
nanocomposites
anode to reduce the battery weight. Various nano compounds and nanocomposites
are being explored as a potential cathode material. Specific materials include carbon fibers, are being explored
carbon as
a potential cathode
nanotubes, material. According
and graphene. Specific materials
to theinclude
currentcarbon fibers, carbon
development nanotubes,
trend, flexible and graphene.
batteries are
According to the current development trend, flexible batteries are undergoing an evolution,
undergoing an evolution, from polymer batteries, flexible alkaline batteries, lithium-based batteries from polymer
batteries,
to metal–airflexible alkaline
batteries. batteries,
Currently, lithium-based
ZABs and AABsbatteries to metal–air
are the ideal flexible batteries. Currently,
batteries due to lowZABs and
cost, safe
AABs are the
operation, andideal
highflexible
energybatteries
density due
[19].to low cost, safe operation, and high energy density [19].
Figure
Figure 4.
4. Schematic
Schematicdiagram
diagramofofdifferent MAB
different configurations:
MAB (a) (a)
configurations: multi-cell static
multi-cell configuration,
static (b)
configuration,
flow battery,
(b) flow andand
battery, (c) flexible battery.
(c) flexible battery.
1.4.Technical
1.4 Technicalbarriers
barriers
Although metal–air
Although metal–air batteries
batteries have
have been
been studied
studied for
for many
many years,
years, there
there areare still
still major
major technical
technical
issues to address for practical applications. Metallic anodes face many challenges, such
issues to address for practical applications. Metallic anodes face many challenges, such as corrosion, as corrosion,
hydrogen generation,
hydrogen generation, forming
forming passivation
passivation layers,
layers, dendritic
dendritic formation,
formation, electrode
electrode deformation,
deformation, and and
energy loss
energy loss due
due to
to self-charging.
self-charging. The
The air
air anode
anode has
has many
many obstacles,
obstacles, such
such asas lack
lack of
of efficient
efficient catalysts
catalysts
for both ORR and OER, affecting electrolyte stability due to impurity and dissolved
for both ORR and OER, affecting electrolyte stability due to impurity and dissolved gas, and gas, and gas
gas
diffusion blockage by side reaction products. Electrolyte selection, which is an important
diffusion blockage by side reaction products. Electrolyte selection, which is an important component component
for efficient
for efficient electrochemical
electrochemical reaction,
reaction, also
also poses
poses some
some technical
technical barriers
barriers due
due toto side
side reaction
reaction with
with the
the
anode, reaction with CO from air, and low conductivity. In the following sections,
anode, reaction with CO22 from air, and low conductivity. In the following sections, we will discuss we will discuss
these issues
these issues and
and potential
potential solutions.
solutions.
2. Cathodes
Appl. Sci. 2019, 9, 2787 6 of 22
Appl. Sci. 2019, 9, x FOR PEER REVIEW

2. Cathodes 6 of 22
2.1
2.1.Components
Componentsofofthe
theCathodic
CathodicElectrode
Electrode
On the
thecathode,
cathode, chemistry
chemistry reactions
reactions are and
are ORR ORROER.andThe
OER. The isoxidant
oxidant oxygen is oxygen
from from air
air atmosphere.
atmosphere.
The catalysts The catalyststoare
are required required
lower to lowerofoverpotential
overpotential ORR and OER. of For
ORRanand OER.electrolyte,
aqueous For an aqueous
water
electrolyte,
loss shouldwater loss should
be avoided to keepbe battery
avoidedstability.
to keep battery
Hence, stability. Hence,
the practical the practical
cathode cathode
is composed of isa
composed of a catalyst layer, gas diffusion layer, and current collector, as shown in Figure
catalyst layer, gas diffusion layer, and current collector, as shown in Figure 5. The current collector 5. The
current collector
can be metal andcan be metalMetal
non-metal. and non-metal. Metal current
current collectors collectors
are a porous are a porous
foam-like metal, foam-like
for example,metal,
Ni,
for example, Ni, Cu. Non-metal current collectors are carbon-based material, for example,
Cu. Non-metal current collectors are carbon-based material, for example, conductive carbon paper, conductive
carbon paper,
graphitic fiber graphitic
or carbon fiber
cloth.orGas
carbon cloth.layer
diffusion Gas(GDL)
diffusion
andlayer (GDL) and
the catalysts the catalysts
are also extremelyare also
crucial
extremely
for cathodecrucial for cathode performance.
performance.
Figure 5.
Figure Various cathodic
5. Various cathodic electrode
electrode ofof MABs,
MABs, (A)
(A) metal
metal current
current collector
collector with
with aa gas
gas diffusion
diffusion layer
layer
and coated
and coated catalyst
catalyst facing
facing electrolyte,
electrolyte, (B)
(B) carbon-base
carbon-base current
current collector
collector and
and gas
gas diffusion
diffusion and
and catalyst,
catalyst,
(C) carbon paper-current collector and gas diffusion and catalyst.
(C) carbon paper-current collector and gas diffusion and catalyst.
(1) Gas diffusion layer: In MABs, the GDL has multi-folded functions: supporting of catalyst
(1) Gas diffusion layer: In MABs, the GDL has multi-folded functions: supporting of catalyst
layer; providing oxygen diffusion channels between air and catalyst layer; preventing water getting into
layer; providing oxygen diffusion channels between air and catalyst layer; preventing water getting
battery and electrolyte getting out of battery. To better serve as a bridge between air and catalyst layer,
into battery and electrolyte getting out of battery. To better serve as a bridge between air and catalyst
the GDL should be thin, light, highly porous, and hydrophobic. Figure 4b indicates that the ORR in
layer, the GDL should be thin, light, highly porous, and hydrophobic. Figure 4(b) indicates that the
MABs occurs at the three phase boundaries (oxygen air, liquid electrolyte, and solid catalyst). The GDL
ORR in MABs occurs at the three phase boundaries (oxygen air, liquid electrolyte, and solid catalyst).
can simultaneously provide hydrophilic micro-channels to the liquid electrolyte, and hydrophobic
The GDL can simultaneously provide hydrophilic micro-channels to the liquid electrolyte, and
layers to prevent electrolyte leakage and good properties of gaseous oxygen diffusion [20].
hydrophobic layers to prevent electrolyte leakage and good properties of gaseous oxygen diffusion
(2) Catalyst layer: Since the kinetics for the oxygen reaction is naturally slow, bifunctional catalysis
[20].
is required to improve ORR and OER to improve electrochemical performances of MABs. Based on
(2) Catalyst layer: Since the kinetics for the oxygen reaction is naturally slow, bifunctional
previous researches, platinum (Pt) [21], ruthenium (Ru) oxides, and iridium oxides (Ir) [22] showed
catalysis is required to improve ORR and OER to improve electrochemical performances of MABs.
excellent performance in ORR and OER. Furthermore, nanostructures of the following materials also
Based on previous researches, platinum (Pt) [21], ruthenium (Ru) oxides, and iridium oxides (Ir) [22]
had good catalytic activity, (a) transition metal oxides, MnO, CoO, NiO, etc. [23]; (b) transition metal
showed excellent performance in ORR and OER. Furthermore, nanostructures of the following
hydroxide and sulfide, NiCoFe-LDH (Layered double hydroxides) layered double hydroxides [24];
materials also had good catalytic activity, (a) transition metal oxides, MnO, CoO, NiO, etc. [23]; (b)
(c) spinel compounds, such as CuCo2 O4 [25]; (d) carbon-based materials, such as nitrogen doping
transition metal hydroxide and sulfide, NiCoFe-LDH (Layered double hydroxides) layered double
carbon [26]; (e) nanocomposite materials mixing ORR catalyst Fe-N-C and OER catalyst NiFe [27].
hydroxides [24]; (c) spinel compounds, such as CuCo2O4 [25]; (d) carbon-based materials, such as
nitrogen doping
2.2. Improving ORR carbon [26]; (e) nanocomposite materials mixing ORR catalyst Fe-N-C and OER
and OER
catalyst NiFe [27].
The appropriate catalyst should be designed and applied to maximize catalytic efficiency.
2.2. Improvingcatalysts
Metal-based ORR and possess
OER high catalytic efficiencies due to different crystal structures. Spinel-type
oxide (Ax B3−x O4 ) [28] and perovskite oxides (ABO3 ) [29] are widely used as bifunctional electrocatalysts
The appropriate catalyst should be designed and applied to maximize catalytic efficiency. Metal-
in alkaline electrolytes. Maiyalagan et al. [30] synthesized a spinel-type lithium cobalt oxide LiCoO2 at
based catalysts possess high catalytic efficiencies due to different crystal structures. Spinel-type oxide
(AxB3−xO4) [28] and perovskite oxides (ABO3) [29] are widely used as bifunctional electrocatalysts in
alkaline electrolytes. Maiyalagan et al. [30] synthesized a spinel-type lithium cobalt oxide LiCoO2 at
high-temperature (800 °C, LiCoO2-HT) and low-temperature LiCoO2-LT at 400 °C. LiCoO2-LT adopts
Appl. Sci. 2019, 9, 2787 7 of 22

high-temperature (800 ◦ C, LiCoO2 -HT) and low-temperature LiCoO2 -LT at 400 ◦ C. LiCoO2 -LT adopts
aa lithiated
lithiated spinel
spinel structure [Li22]]16c [Co
[Co2]216dO4Oin4 in
]16d which
which thethe
CoCo 3+ ions
3+ ions occupy all the
occupy all 16d octahedral
the 16d sites
octahedral
16c
(space
sites group:
(space Fd3m)
group: [31].[31].
Fd3m) As shown
As shown in Figure
in Figure6(a),
6a,LiCoO
LiCoO22-HT-HThas
has the
the α-NaFeO22 structure (space
(space
group: R3m)
group: R3m) arrays.
arrays. LiLi++ ions and Co Co3+
3+ ion
ion occupy on alternate (111) (111) NaFeO
NaFeO22-style structure arrays,
arrays,
due to
due to the
the large
large size
size and
and charge
charge differences
differences between
between the Li++ and Co3+
the Li 3+ ions
ions[32].
[32].InInFigure
Figure6(b),
6b, itit isis
obviousthat
obvious thatHT-LCoO
HT-LCoO22 has has aa better
better catalytic
catalytic performance
performancethan thanLT-LiCoO
LT-LiCoO22andandCo Co33OO44.
Catalysts are
Catalysts are preferred
preferred at at nanoscale
nanoscale for for better
better catalytic
catalytic behavior.
behavior. ByBy using
using aa vacuum
vacuum DCDC arcarc
method,Lang
method, Langet etal.
al. [33]
[33] synthesized
synthesizedaa novel novel Mn /MnO nano spherical transition metal compound.
Mn33O44/MnO
The results
The results showed
showed thatthat the
the size
size of
of Mn
Mn33O /MnO particles was controlled at a range of 40 to 60 nm.
O44/MnO
TheMn
The Mn33O O44/MnO
/MnO catalyst potential platform reaches reaches to to 2.7
2.7 V.
V.
Figure6.6. (a)
Figure (a) X-ray
X-raydiffraction
diffractionpatterns
patternsand
and(b)
(b)electrochemical
electrochemicalbehaviors
behaviorsofofCo
Co3 O
3O44,, low-temperature
low-temperature
(LT)-LiCoO , high-temperature (HT)-LiCoO catalysts [30] (Copyright © 2014, Springer
(LT)-LiCoO2, high-temperature (HT)-LiCoO2 catalysts [30] (Copyright © 2014, Springer Nature).
2 2 Nature).
Nanoscale
Nanoscale catalysts
catalysts can can also
also bebe fabricated
fabricated with
with various
various other
other morphologies,
morphologies, such such as as nano-rod
nano-rod
LaCoO
LaCoO33 [34], 3D ordered mesoporous structure Co33O44 [35], hollow cobalt oxide nanoparticles [36].
[34], 3D ordered mesoporous structure Co O [35], hollow cobalt oxide nanoparticles [36].
Different morphologies of catalysts are shown in Figure 7. Many low-cost and
Different morphologies of catalysts are shown in Figure 7. Many low-cost and efficient catalysts have efficient catalysts have been
developed,
been developed, including transition
including metals and
transition nitrogen
metals co-dopedco-doped
and nitrogen carbons (M-N/C,
carbonsM=Fe (M-N/C,or Co) [25],or
M=Fe metal
Co)
oxides [37], transition metal carbides [38], nitrides [39], and metal-free heteroatom-doped
[25], metal oxides [37], transition metal carbides [38], nitrides [39], and metal-free heteroatom-doped carbon-based
catalysts
carbon-based [40]. Compared
catalysts [40]. to metal-contained catalysts, the heteroatom-doped
Compared to metal-contained carbon-based materials
catalysts, the heteroatom-doped carbon-
with N, S, B, and P, can promote oxygen adsorption on the
based materials with N, S, B, and P, can promote oxygen adsorption on the carbon carbon nanostructure since thesenanostructure
hetero-atoms
are more
since these electronegative
hetero-atoms than carbon,
are more and cause neighboring
electronegative than carbon,carbon atoms
and cause electron deficiency
neighboring carbon atoms[41].
Among
electronthem, N-doped
deficiency carbons
[41]. Among are extensively
them, N-doped studied due to are
carbons theirextensively
remarkable studiedORR catalyticdue toactivity.
their
N-doped carbon materials are shown in four ways, graphitic N, Oxidized
remarkable ORR catalytic activity. N-doped carbon materials are shown in four ways, graphitic N, N, pyrrolic N, and pyridic N
in Figure 8.N, pyrrolic N, and pyridic N in Figure 8.
Oxidized
Although
Althoughseveral several materials
materials havehave shown
shown catalytic
catalytic activity
activity for
for oxygen
oxygen reaction
reaction in in MABs
MABs cathodes,
cathodes,
the catalytic efficiency is not ideal when used alone. To
the catalytic efficiency is not ideal when used alone. To improve comprehensive improve comprehensive catalyst performance,
catalyst
composition materials have been synthesized and used as catalysts
performance, composition materials have been synthesized and used as catalysts in both ORR in both ORR and OER. MnO 2 and
and
RuO are single catalysts for ORR and OER, respectively.
OER.2 MnO2 and RuO2 are single catalysts for ORR and OER, respectively.2 Combining Combining MnO with RuO is used
2 MnO2 with as a
bifunctional
RuO2 is used catalyst. Sun et al. [42]
as a bifunctional synthesized
catalyst. Sun et RuO 2 nanoparticles
al. [42] synthesized(np-RuO 2 /nr-MnO2 ) supported
RuO2 nanoparticles (np-RuO2/nr- on
MnO
MnO22)nanorods
supported by aon two-step
MnO2hydrothermal
nanorods byreaction. a two-stepElectrochemical
hydrothermal characterizations are carried on
reaction. Electrochemical
nanocomposites np-RuO
characterizations are carried 2 /nr-MnO 2 as catalysts
on nanocomposites for LABs. Charge–discharge tests
np-RuO2/nr-MnO2 as catalysts for LABs. showed a reversible
Charge–
discharge capacity of 500 mAh g −1 for 75 cycles at a current density of 50 mA g −1 . LABs with the
discharge tests showed a reversible discharge capacity of 500 mAh g for 75 cycles at a current −1
RuO 2 /MnO 2 catalyst presented much lower overpotential of 0.58
density of 50 mA g . LABs with the RuO2/MnO2 catalyst presented much lower overpotential of
−1 V at 50 mA g −1 than that measured
with
0.58 Va atsingle
50 mA catalyst.
g−1 thanORR and OER electrocatalytic
that measured activity
with a single catalyst. were
ORR andtested
OER by using rotating
electrocatalytic disk
activity
electrodes.
were testedItby was found
using that np-RuO
rotating 2 /nr-MnO2ItORR
disk electrodes. waslimitation
found that diffusion
np-RuOcurrent was 6.01 mA cm−2 ,
2/nr-MnO2 ORR limitation
and ORR half-wave
diffusion current was potential
6.01 mA(Ecm , and−0.158
1/2 )−2was V. These results
ORR half-wave demonstrated
potential (E1/2) was -0.158that an V.np-RuO 2 and
These results
nr-MnO 2
demonstrated combination can work as an effective catalyst for LABs with high
that an np-RuO2 and nr-MnO2 combination can work as an effective catalyst for LABs activity while maintaining
batteries
with high stability.
activity while maintaining batteries stability.
Appl. Sci. 2019, 9, 2787 8 of 22
Appl. Sci.
Appl. Sci. 2019,
2019, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 88 of
of 22
22
Figure 7.7. (a)

(a) SEM
SEM images
images of Mn Mn3O44/MnO
/MnO nanoparticles
nanoparticles [33]
[33] (Copyright
(Copyright ©
© 2019, Elsevier),
Elsevier), (b)
(b) TEM
TEM
Figure 7. (a) SEM images of of Mn3 O43O /MnO nanoparticles [33] (Copyright © 2019, 2019,
Elsevier), (b) TEM images
images
images of LaCoO
of3 LaCoO 3 catalysts [34], (c) TEM image of honeycomb-like 3D ordered mesoporous spinel
3 catalysts [34], image
(c) TEM image of honeycomb-like
of LaCoO catalysts [34], (c) TEM of honeycomb-like 3D ordered3D ordered mesoporous
mesoporous spinel Co3 Ospinel
4 [35]
Co O44 [35]
Co33O
(Copyright[35] © (Copyright
(Copyright
2016, John© ©Wiley
2016,and
2016, John
John Wiley
Wiley
Sons), and Sons),
(d) and
TEM Sons), (d)
image (d) TEM image
TEM
of hollow image of hollow
cobalt of hollow
oxide cobalt oxide
cobalt
nanoparticles oxide
[36]
nanoparticles [36] (Copyright
(Copyright © 2019, Elsevier).
nanoparticles [36] (Copyright ©
© 2019,
2019, Elsevier).
Elsevier).
Figure 8.
Figure
Figure 8. Four
8. nitrogen doping
Four nitrogen
nitrogen doping configurations
doping configurations of
configurations of aaa graphene
of graphene molecule
graphene molecule [23].
molecule [23].
[23].
2.3. In
2.3. In Situ
In Situ Characterization
Situ Characterization Using
Characterization UsingUsing an an Electron
an Electron Microscope
Electron Microscope
Microscope
2.3.
An
An in in situ
situ electron
electron microscope
microscope is is aaa promising
promising tool tool for
for scientific
scientific research
research duedue to to real-time
real-time
An in situ electron microscope is promising tool for scientific research due to real-time
observation
observation and and plays
and plays a major
plays aa major role
major role in
role in many
in many
many MAB MAB studies,
MAB studies, such
studies, such
such as as the
as the catalytic
the catalytic mechanism,
mechanism, the
catalytic mechanism, the
observation the
oxidation–reduction
oxidation–reduction mechanism,
mechanism, the
the growth
growth of
of nanostructures,
nanostructures, and
and the
the deformation
deformation of
of electrodes.
electrodes.
oxidation–reduction mechanism, the growth of nanostructures, and the deformation of electrodes.
Based
Based on on the
the distinctive
distinctive features
features of of the
the preceding,
preceding, Katharine
Katharine et et al.
al. [43]
[43] found
found thatthat higher
higher Coulombic
Coulombic
Based on the distinctive features of the preceding, Katharine et al. [43] found that higher Coulombic
efficiency
efficiency and and more
and more homogeneous
more homogeneous
homogeneous morphology morphology
morphology of of
of thethe
the Li Li deposits
Li deposits
deposits in in a coin-cell
in aa coin-cell contributed
coin-cell contributed
contributed to to theto
the
efficiency
the presence
presence of of a compressed
of aa compressed
compressed lithium lithium separator
lithium separator interface
separator interface through
interface through
through in in situ
in situ electrochemical-scanning
situ electrochemical-scanning
electrochemical-scanning
presence
transmission microscope
transmission microscope (EC-STEM),
microscope (EC-STEM), compared
(EC-STEM), compared with
compared with a macroscale
with aa macroscale cell.
macroscale cell. In addition,
cell. In
In addition,YoonYoon
addition, et al. et
[44]
al.used
[44]
transmission Yoon et al. [44]
in situinatomic
used situ force microscope
atomic force (AFM) (AFM)
microscope to measureto the dominant
measure the wavelength
dominant of the wrinkled
wavelength of the surface
wrinkled
used in situ atomic force microscope (AFM) to measure the dominant wavelength of the wrinkled
topography. The planes
surface topography.
topography. Thestrain
planes modulus of
strain modulus the SEI was
modulus of the determined
the SEI was from the measured
was determined
determined from the
thewavelength.
measured
surface The planes strain of SEI from measured
Li et al. [45]
wavelength. Li explored
Li et
et al. the
al. [45] reaction
[45] explored
explored the mechanism
the reaction and
reaction mechanismunveiled
mechanism and that α-MoO
and unveiled
unveiled that 3 converted
that α-α- MoO to crystalline
MoO33 converted
converted to to
wavelength.
Li 2 MoO3 in Li
crystalline the first stage of lithiation, and further converted to metallic Mo and amorphous Li O in
2MoO3 in the first stage of lithiation, and further converted to metallic Mo2 and
crystalline Li2MoO3 in the first stage of lithiation, and further converted to metallic Mo and
the next stage.
amorphous Asinshown
Li22O
O the next in stage.
next FigureAs 9a,shown
with ainnegative
Figure 9(a),potential
9(a), with aato the Au/MnO
negative 2 nanowires
potential to the (NWs),2
the Au/MnO
Au/MnO
amorphous Li in the stage. As shown in Figure with negative potential to 2
nanowires (NWs), bubble-like NaO 2 nucleated on the contact where the Au/MnO2 NW and Na2O
nanowires (NWs), bubble-like NaO2 nucleated on the contact where the Au/MnO2 NW and Na2O
intersects, then
intersects, then grows
grows along
along the
the NW,NW, resulting
resulting in in 18
18 times
times volume
volume increase.
increase. Meanwhile,
Meanwhile, the the discharge
discharge
Appl. Sci. 2019, 9, 2787 9 of 22

bubble-like NaO2 nucleated on the contact where the Au/MnO2 NW and Na2 O intersects, then grows
along
productthe shrinks
NW, resulting in 18 of
as a result times
thevolume increase. Meanwhile,
disproportionation of NaO2 the discharge
to Na 2O2 andproduct shrinks asthe
O2, confirming a
result of theof
occurrence disproportionation
ORR [46]. Similarly, of NaO
Liu et2 to
al.Na 2 Oalso
[47] 2 and O2 , confirming
reported the occurrence
the real-time observation of of
ORR
ORR [46].
in
Figure 9(b).
Similarly, LiuInetthis research,
al. [47] CuO nanowires
also reported (NWs),
the real-time as the air cathode,
observation of ORR infirstly converted
Figure to Cu
9b. In this 2O and
research,
then nanowires
CuO to Cu, as a(NWs),
metal catalyst tocathode,
as the air accelerate the disproportionation
firstly converted to Cu2 O and of NaO Na2O
then2 to Cu, as2 aand
metalO2.catalyst
During
theaccelerate
to reaction process, the morphological
the disproportionation of changes
NaO2 towere Na2investigated
O2 and O2 . by an electrochemical
During atomic force
the reaction process, the
microscope. Liu
morphological changeset were
al. [48] used EC-AFM
investigated to observe
by an electrochemical the force
atomic dynamic process
microscope. of al.Li[48]
Liu et 2O2
growth/decomposition
used EC-AFM to observeduring the ORR/OER
the dynamic process on of Lia 2gold electrode in Figure 9(c)
O2 growth/decomposition and found
during that the
the ORR/OER
on a 2gold
Li2O electrode inatFigure
decomposed 9c and
a lower found that
potential due theto Li 2 O2 decomposedgenerated
electrochemically at a lower TTF
potential due toa
+ through
electrochemically generated TTF + through a homogeneous oxidation mechanism.

homogeneous oxidation mechanism.
Figure 9.9. (a)

Figure (a) Structure
Structure evolution
evolution of
of the
theNaO
NaO22 discharge
discharge product
product during
during oxygen
oxygen reduction
reduction reaction
reaction
(ORR)[46]
(ORR) (Copyright©
[46](Copyright © 2019,
2019, Elsevier);
Elsevier); (b)
(b) Structural
Structural and
and phase
phase characterization
characterizationof
ofaa CuO
CuO nanowire
nanowire
(NW) during
(NW) during discharging
discharging and
and charging
charging ininan environment [47]
anOO2 2 environment (Copyright©
2018, American
American
ChemicalSociety);
Chemical Society);(c)
(c)Cyclic
Cyclicvoltammetry
voltammetryperformed
performedin inelectrochemical-atomic
electrochemical-atomicforce
forcemicroscope
microscopecell
cell
andthe
and theresulting
resultingAFMAFMimage
imageafter
afterCV
CVreduction
reduction[48] (Copyright©
2016, American
American Chemical
Chemical Society).
Society).
3. Anodes
3. Anodes
The chemical activity of the metal anode determines the discharge capacity. Because of high
The chemical activity of the metal anode determines the discharge capacity. Because of high
metal activity, an unavoidable side reaction with various components in the electrolyte may occur.
metal activity, an unavoidable side reaction with various components in the electrolyte may occur.
Depending on the purity of the metal, the battery performance and the incidence of side reactions can
Depending on the purity of the metal, the battery performance and the incidence of side reactions
be different.
can be different.
3.1. Anode Materials: High Purity Metal and Alloy
3.1. Anode Materials: High Purity Metal and Alloy
Fan et al. [49] took industrial 5 N Al (99.999% high purity) and aluminum alloy (1050, 2011, 3003,
Fan et al. [49] took industrial 5 N Al (99.999% high purity) and aluminum alloy (1050, 2011, 3003,
4032, 5052, 6061, 7050, and 8011) as anodes for AABs in alkaline electrolytes, using the hydrogen
4032, 5052, 6061, 7050, and 8011) as anodes for AABs in alkaline electrolytes, using the hydrogen
collection method and electrochemical impedance spectroscopy (EIS) to determine the corrosion
collection method and electrochemical impedance spectroscopy (EIS) to determine the corrosion
behaviors, electrochemical properties, and potentiodynamic polarization. Test results of corrosion and
behaviors, electrochemical properties, and potentiodynamic polarization. Test results of corrosion
EIS showed the sample in 4 M KOH was more suitable than in 4 M NaOH. Al 8011 had a transfer
and EIS showed the sample in 4 M KOH was more suitable than in 4 M NaOH. Al 8011 had a transfer
resistance (Rt ) of 1.247 Ω cm2 in 4 M NaOH and 1.108 Ω cm2 in 4 M KOH. 5 N Al had Rt of 2.29 Ω cm2
resistance (Rt) of 1.247 Ω cm2 in 4 M NaOH and 1.108 Ω cm2 in 4 M KOH. 5 N Al had R of 2.29 Ω cm2
in 4 M NaOH and 15.3 Ω cm2 in 4 M KOH. 5 N Al had 1.699 V Ecorr in 4M NaOH andt 1.821 V Ecorr
in 4M
in 4 MKOH.
NaOH Alland 15.3 Ω cm
industrial
2 in 4 M KOH. 5 N Al had 1.699 V Ecorr in 4M NaOH and 1.821 V Ecorr in
Al alloy anodes had the hydrogen adsorption phenomenon of hydrogen
4M KOH. All industrial Al alloy anodes had the hydrogen adsorption phenomenon of hydrogen
evolution reaction, and 8011 had relatively better performance than the others. As shown in Table 1,
Al 8011 had a lower corrosion potential (Ecorr) at −1.42 V, corrosion current (Icorr), of 135 mA cm−2, and
Appl. Sci. 2019, 9, 2787 10 of 22
evolution reaction, and 8011 had relatively better performance than the others. As shown in Table 1,
Al 8011 had a lower corrosion potential (Ecorr ) at −1.42 V, corrosion current (Icorr ), of 135 mA cm−2 , and
polarization resistance (Rp ) of 3.628 Ωcm2 among industrial Al alloys. Therefore, impurity elements
had different roles in the corrosion behaviors. Mg, Mn, Cr, Ti, and Zn were helpful to improve
the corrosion resistance of Al alloy anodes, while Fe, Cu, and Si formed cathodic sites and lowered
overpotential for hydrogen evolution reaction (HER) [49–51]. Different components Al alloys (Zn-rich
and Al-rich phases) worked as abode AABs anode. Test results showed Al-rich alloys were better
performance, due to lower the anodic passivation. Zn-Al alloys are promising anode materials as
primary and mechanical-rechargeable Zn-air batteries [52].
Table 1. Parameters and electrochemical impedance spectroscopy (EIS) value of different grades of Al
anodes [49].
Ecorr (V vs. Hg/HgO) Icorr (mA cm−2 ) Rp (Ω cm2 )

Grade
4 M NaOH 4 M KOH 4 M NaOH 4 M KOH 4 M NaOH 4 M KOH
1050 1.290 1.291 186 176 4.108 5.683
2011 1.410 1.420 135 142 4.124 6.674
3003 1.315 1.340 181 165 4.607 5.892
4032 1.390 1.390 145 174 4.653 2.572
5052 1.310 1.320 191 157 3.766 2.539
6061 1.370 1.380 161 168 4.766 2.655
7050 1.420 1.450 189 143 4.516 2.848
8011 1.420 1.450 135 144 3.628 2.670
5N 1.699 1.821 24.3 4.7 9.668 17.9
Grade
Equivalent
solution 1050 2011 3003 4032 5052 6061 7050 8011 5N
elements
4 M NaOH 0.70 0.75 0.57 0.84 0.74 0.49 0.76 1.247 2.29
Rt (Ω cm2 )
4 M KOH 1.23 0.69 1.208 0.3351 0.78 0.36 0.60 1.108 15.3
3.2. Metal Coating and Composite Electrodes

Different from previous research using Al alloy as anodes, Mutlu [53] investigated Cu coating
on Al and 7075 Al alloy as anodes. Copper was deposited on the Al surface by chemical (Al or
Alloy/Cu-CD) and electrochemical (Al or Alloy/Cu-ED) processes, SEM images are shown in the
Figure 10a,b. Al has a lower resistance than Al-Cu alloy. EIS measurements showed that copper
on the Al surface could decrease anodic potential and improve batteries performance as shown in
Figure 10c,d. The solution–electrode interaction resistance (Rs) was increased by adding copper to
aluminum because copper can form a protective layer against the corrosion on the aluminum–solution
interface. Hang et al. [54] found that FeS can employ as an additive for the electrode to suppress
hydrogen evolution and improve the cyclic performance of the Fe/C composite anode. FeS additive
and the carbon component also strongly affected the redox behavior of iron. An electrode with FeS
can promote the process (in the Figure 11) of Fe0 to Fe2++ and Fe2+ to Fe3+ at around −0.85 V (a1 ),
−0.65 V (a2 ), respectively. Furthermore, there were also additional intermediate species which appeared
around −0.97 V (a0 ). The discharge capacity of the electrode was significantly improved with adding
2 wt.% FeS, which was mainly because the incorporation of FeS in the electrode improved the adsorbed
capability of S2− on the electrode surface, resulting in the easy breaking of the oxide layer. For HER
at the anode in alkaline electrolyte, both molecular recombination and electrochemical desorption
can be parallel steps in the overall process. The molecular recombination reaction will appreciably
contribute to HER only when the current density is low, and the molecular hydrogen concentration
at the liquid boundary layer is near to zero. Under these conditions, it has been indicated that the
molecular recombination reaction is affected by S2− ion chemisorption.
Appl.hydrogen
Sci. 2019, 9,concentration
2787 at the liquid boundary layer is near to zero. Under these conditions, it has
11 of 22
hydrogen
been concentration
indicated at the liquid
that the molecular boundary layer
recombination is near
reaction to zero.by
is affected Under these
S2− ion conditions, it has
chemisorption.
been indicated that the molecular recombination reaction is affected by S2− ion chemisorption.
Figure 10. SEM images and EDS maps of (a) Al/Cu-CD, (b) Al/Cu-ED, (c) The cyclic voltammogram
Figure 10. SEM imagesandandEDSEDSmaps
maps of (a)
(a) Al/Cu-CD,
Al/Cu-CD, (b)(b)Al/Cu-ED,
Al/Cu-ED,(c)(c)
The cyclic voltammogram
Figure 1 MSEM
in10. NaOH images
of Al (pure), Al/Cu-CD,of
and Al/Cu-ED, (d) EIS measurements ofThe cyclic
anodes in 1voltammogram
M NaOH,
in 1
in 1 MTheM NaOH
NaOH of
of AlAl (pure),
(pure), Al/Cu-CD, and Al/Cu-ED, (d) EIS measurements of anodes in 1inM1NaOH,
Nyquist a Al (pure),Al/Cu-CD, and Al/Cu-ED,
Al/Cu-CD, Al/Cu-ED (d) EIS measurements
[53] (Copyright © 2018, Springer of anodes
Nature). M NaOH,
The Nyquist a Al (pure), Al/Cu-CD, Al/Cu-ED [53] (Copyright © 2018, Springer Nature).
The Nyquist a Al (pure), Al/Cu-CD, Al/Cu-ED [53] (Copyright © 2018, Springer Nature).
(a) (b)
(a) (b)
FigureFigure 11. Cyclic
11. Cyclic voltammetry
voltammetry for Fe/C
for Fe/C composite
composite electrodes
electrodes composited
composited carbon
carbon nano-fibers
nano-fibers (a)(a)
without
without
andFigure
(b) with and
11.FeS (b) with
additive
Cyclic FeS additive [54] (Copyright
for Fe/C©
[54] (Copyright
voltammetry © 2006, Elsevier).
2006, Elsevier).
composite electrodes composited carbon nano-fibers (a)
without and (b) with FeS additive [54] (Copyright © 2006, Elsevier).
3.3. Common
3.3. Common Challenge
Challenge of Metal
of Metal Anode
Anode
3.3.
TheCommon
commonChallenge
The common
issuesof with
Metal
issues withAnode
metallicanodes
metallic anodes are
are corrosion,
corrosion,passivation,
passivation,andand
dendrite formation.
dendrite formation.
These mechanisms are displayed in Figure 12.
These mechanisms
The commonare displayed
issues in Figure
with metallic 12. are corrosion, passivation, and dendrite formation.
anodes
Corrosion: Corrosion is one of the major side reactions between metal and electrolyte, and its
Corrosion:
These Corrosion
mechanisms is one of
are displayed in the major
Figure 12. side reactions between metal and electrolyte, and its
reaction can be expressed as follows:
reactionCorrosion: Corrosion
can be expressed as is one of the major side reactions between metal and electrolyte, and its
follows:
reaction can be expressed as follows:M + (2 + x)H2O ⇌ 2M(OH) + H2 (19)
+ (2
MM + x)H
+ (2M+ +x)H
O⇌
H22O
MO X + H 2 + H2
2M(OH)
2O ⇌ 2M(OH) + H2
(20)
(19)
(19)
Equation (19, 20) evaluates the corrosion rate due to hydrogen evolution reaction (HER). For
MM+ +HH2 O
2O
⇌MOMOX + +HH22 (20) (20)
almost all MABs, the M/MO standard voltage was belowX that of the hydrogen revolution. Therefore,
Equation(19)
hydrogen
Equations (19,and
20) (20)
evolution evaluates the corrosion
wasevaluates
spontaneously rate due
favored.
the corrosion ratetoHER
The hydrogen
due decreased
to evolution
hydrogen metal reaction (HER). For
anode Coulombic
evolution reaction (HER).
almost all MABs,
efficiency the itM/MO
because standard
consumed voltage
electrons fromwas
thebelow
metal that of in
anode thethe
hydrogen revolution.hydrogen
charge. Moreover, Therefore,
For almost all MABs, the M/MO standard voltage was below that of the hydrogen revolution. Therefore,
hydrogen evolution was spontaneously favored. The HER decreased metal anode Coulombic
hydrogen evolution was spontaneously favored. The HER decreased metal anode Coulombic efficiency
efficiency because it consumed electrons from the metal anode in the charge. Moreover, hydrogen
because it consumed electrons from the metal anode in the charge. Moreover, hydrogen diffusing into
electrolyte leads to the increase of internal battery pressure and could result in an explosion.
Hydrogen evolution reaction: Hydrogen evolution reaction (HER) was a side reaction of metal
electrodes during the charge–discharge of batteries. The specific working principle is shown in
Equations (19) and (20). Metal releases electrons to the aqueous electrolyte system and hydrogen ions
Appl. Sci. 2019, 9, 2787 12 of 22
replace metal ions obtaining electron reduction in hydrogen. HER in MABs thus influences the rates of
metal electrodes. Hydrogen overpotential decreases on the ZnO surface since the self-discharge rate
reducedAppl.
withSci.increasing
2019, 9, x FORZnO on the electrode surface [55]. Increasing overpotential of HER
PEER REVIEW 12 (decreased
of 22
HER rate) can thus improve the charging efficiency. In addition, the corrosion and oxidation of Al in
diffusing into electrolyte leads to the increase of internal battery pressure and could result in an
alkaline explosion.
electrolytes depend on electrolyte properties, temperature, and purity [56]. Using ionic liquid
or solid stateHydrogen
electrolyte is an effective
evolution solution to
reaction: Hydrogen reducereaction
evolution the HER rate,
(HER) which
was a sidehas beenofconfirmed
reaction metal in
FABs [57]. An alloy
electrodes duringas anodes replacing pure
the charge–discharge metal also
of batteries. Thereduced the corrosion
specific working principlerate, and additives,
is shown in
such as Equation
bismuth(19,20).
or sulfur,Metal releases
could electronsthe
minimize to corrosion
the aqueousofelectrolyte
the iron system
electrodeandand
hydrogen ions
the evolution of
replace
hydrogen [58]. metal ions obtaining electron reduction in hydrogen. HER in MABs thus influences the rates
12. Corrosion,
Figure Figure passivation,
12. Corrosion, and
passivation, anddendrite formation
dendrite formation processes
processes at a at a metal
metal anode.anode.
Passivation layers: Passivation

of metal electrodes. used to describe
Hydrogen overpotential an electrode
decreases on the ZnOthat could
surface notthe
since beself-discharge
further discharged
because an insulating film on its surface blocked migration of the discharge product. In of
rate reduced with increasing ZnO on the electrode surface [55]. Increasing overpotential HER LiOH,
MABs,
(decreased HER rate) can thus improve the charging efficiency.
ZnO, and Al2 O3 were passivation layers for corresponding systems. Soluble species formed In addition, the corrosion and at the
oxidation of Al in alkaline electrolytes depend on electrolyte properties, temperature, and purity [56].
air cathode will be reduced to a non-conductive layer on the metal surface. This a non-conductive
Using ionic liquid or solid state electrolyte is an effective solution to reduce the HER rate, which has
layer increases the internal
been confirmed in FABselectrical resistance
[57]. An alloy as anodesof the cell and
replacing pureprevents
metal alsometal
reduced dissolution.
the corrosionThe
rate,efficient
method andis toadditives,
use porous electrodes to hinder the formation of passivation layers.
such as bismuth or sulfur, could minimize the corrosion of the iron electrode and the
Dendritic
evolutionformation [58]. deformation: During the metal electrode cycling in an alkaline
of hydrogen and
Passivation layers:
electrolyte, the metal anode releases Passivation used
ions to describe
during dischargean electrode
and thethat metalcould
ionsnotre-deposit
be further on the
discharged because an insulating film on its surface blocked migration of the discharge product. In
surface of the anode during charging. As a result, the metal electrode will gradually change shape, and
MABs, LiOH, ZnO, and Al2O3 were passivation layers for corresponding systems. Soluble species
its surface will become roughened with uneven thicknesses. Over several charge and discharge cycles,
formed at the air cathode will be reduced to a non-conductive layer on the metal surface. This a non-
the uneven shapelayer
conductive accumulates
increases theto internal
form dendrites, causingofthe
electrical resistance thebattery system metal
cell and prevents to become unstable or
dissolution.
short cut. Different approaches have been attempted to mitigate dendritic formation
The efficient method is to use porous electrodes to hinder the formation of passivation layers. and deformation,
such as coatingDendritic
the zincformation
metal and andusing
deformation: During
non-reaction the metal
additives inelectrode cycling in or
the zinc electrode an electrolyte
alkaline [59].
electrolyte, the metal anode releases ions during discharge and the
Lithium alloying with Na [60], Mg [61], Al [62] has been confirmed to effectively suppress metal ions re-deposit onthe
thegrowth
surface of the anode during charging. As a result, the metal electrode will gradually change shape,
of dendritic Li.
and its surface will become roughened with uneven thicknesses. Over several charge and discharge
In summary, passivation
cycles, the uneven shapelayers happen
accumulates to in
formAABs, ZABs,
dendrites, and LABs,
causing dendritic
the battery systemstructures
to becomeform in
ZABs, and LABs and FABs, and corrosion may occur in FABs, AABs, ZABs,
unstable or short cut. Different approaches have been attempted to mitigate dendritic formation andand LABs. Different
strategies are needed
deformation, to as
such address
coatingthese issues.
the zinc metal and using non-reaction additives in the zinc electrode or
electrolyte [59]. Lithium alloying with Na [60], Mg [61], Al [62] has been confirmed to effectively
4. Electrolytes
suppress the growth of dendritic Li.
In summary, passivation layers happen in AABs, ZABs, and LABs, dendritic structures form in
An ZABs,
electrolyte is a medium
and LABs to transport
and FABs, ionsmay
and corrosion and occur
electrons to ensure
in FABs, AABs,the continued
ZABs, oxidation–reduction
and LABs. Different
reaction.strategies
Electrolyte dividedtointo
are needed fourthese
address types: aqueous, non-aqueous, hybrid, and solid state, as shown in
issues.
Figure 13.
4. Electrolytes
An electrolyte is a medium to transport ions and electrons to ensure the continued oxidation–
reduction
Appl. Sci. reaction. Electrolyte divided into four types: aqueous, non-aqueous, hybrid, and solid state,
2019, 9, 2787 13 of 22
as shown in Figure 13.
Figure Schematic
13.13.
Figure Schematicdiagrams of various
diagrams of variouselectrolytes
electrolytesof of MABs.
MABs.
4.1. Aqueous Electrolyte

4.1. Aqueous Electrolyte
Alkaline
Alkalinesolutions (7 <
solutions < pH≤ ≤14):
(7 pH 14): Alkaline electrolytesare
Alkaline electrolytes arethethe most
most applied
applied electrolyte
electrolyte in in
aqueous-based
aqueous-based MABs, MABs, because
because theORR
the ORRisismore
more favorable
favorable with
withfaster
fasterreaction kinetics
reaction and and
kinetics a lower
a lower
overpotential,
overpotential, compared
compared to to acidicelectrolytes.
acidic electrolytes. Alkaline
Alkaline electrolytes
electrolytes have
havea shortcoming
a shortcoming that that
CO2 CO
2
(from air atmosphere) reacts with electrolyte and forms a carbonate surrounding
(from air atmosphere) reacts with electrolyte and forms a carbonate surrounding the cathode. The the cathode. The large
large amount of carbonate will block the porous structure of the positive electrode material and
amount of carbonate will block the porous structure of the positive electrode material and decrease
decrease cathode efficiency.
cathode efficiency.
Neutral salt solution (pH = 7): Al alloy–air batteries can discharge in a neutral salt solution with
Neutral salt solution
a lower corrosion (pH
rate and = 7): activity
higher Al alloy–air
than inbatteries canelectrolyte.
an alkaline discharge in a neutral salt solution with
a lower corrosion rate and
Acidic solutions (2 higher activity
≤ pH < 7): than in an alkaline
Acidic electrolytes are rarelyelectrolyte.
used in aqueous-based MABs because
Acidic amount of (2
a large solutions H+≤in pH < 7): Acidic
solution could electrolytes
directly reactare rarely
with used
metal andinreducing
aqueous-based
battery MABs because
efficiency.
a large amount
Saidman et al. H+ reported
of[63] in solutionAl-Zncould
alloy directly react withchanged
anode performance metal andwith reducing battery
various types efficiency.
of acids at
the same concentration, pH, and operating temperature. Electrochemical test results
Saidman et al. [63] reported Al-Zn alloy anode performance changed with various types of acids at the indicted Al–Zn
samealloy in 0.5 M HCl
concentration, was
pH, more
and negativetemperature.
operating than that in 0.5Electrochemical
M HAc: −1.02 V and test−0.80 V, respectively.
results indicted Al–Zn alloy
Hybrid electrolyte: In Figure 14(b), (c), a novel type of aqueous FABs was equipped with an
in 0.5 M HCl was more negative than that in 0.5 M HAc: −1.02 V and −0.80 V, respectively.
alkaline anode electrolyte (anolyte) and an acidic cathode electrolyte (catholyte). The anolyte and
Hybrid electrolyte: In Figure 14b,c, a novel type +of aqueous FABs was equipped with an alkaline
catholyte are separated by an alkali metallic ion (Li or Na+) solid-state electrolyte separator. The
anode electrolyte (anolyte) and an acidic cathode electrolyte (catholyte). The anolyte and catholyte are
alkali metal ion serves as an ionic mediator to sustain the redox reactions at both the anode and
separated
cathode an alkali metallic ion (Li+ or Na+ ) solid-state electrolyte separator. The alkali metal ion
by[64].
serves asSci.
Appl. an2019,
ionic9, xmediator to sustain the redox reactions at both the anode and cathode [64].
FOR PEER REVIEW 14 of 22
Figure 14. (a)

Figure 14.Schematic illustration
(a) Schematic of theoretical
illustration voltages
of theoretical of Fe−air
voltages batteries
of Fe−air operated
batteries with
operated an alkaline
with an
or analkaline or an acidic
acidic cathode cathode electrolyte.
electrolyte. Two types Two types batteries
of Fe−air of Fe−air with
batteries
a Na + - or
with aa Li+-+or
Na a Li
-ion +-ion solid
solid electrolyte,
2 (H3 PO4 /LiH2 PO4 ) cell, and (c) a Fe(NaOH)//Na-SS//O2 (H3 PO4 /NaH2 PO4 )
electrolyte,
for (b) for (b) a Fe(LiOH)//Li-SSE//O
a Fe(LiOH)//Li-SSE//O 2(H3PO4/LiH2PO4) cell, and (c) a Fe(NaOH)//Na-
SS//O 2(H3PO4/NaH2PO4) cell. SSE represents solid-state electrolyte [64] (Copyright © 2017, American
cell. SSE represents solid-state electrolyte [64] (Copyright © 2017, American Chemical Society).
Chemical Society).
4.2. Non-Aqueous Electrolyte

Solid-state electrolyte: Solid-state electrolytes are different from aqueous electrolytes in dual
characteristics of wettability and ion conduction. For MABs, aqueous electrolytes with an excellent
wetting property at three-phase boundaries could be in full contact with the cathode. For a solid-
based electrolyte, the three-phase interface reaction can be restricted by the poor wetting property of
−
Appl. Sci. 2019, 9, 2787 14 of 22
4.2. Non-Aqueous Electrolyte

Solid-state electrolyte: Solid-state electrolytes are different from aqueous electrolytes in dual
characteristics of wettability and ion conduction. For MABs, aqueous electrolytes with an excellent
wetting property at three-phase boundaries could be in full contact with the cathode. For a solid-based
electrolyte, the three-phase interface reaction can be restricted by the poor wetting property of the
“immobilized” electrolyte, thereby, interfacial transporting resistance of OH− may be remarkably higher
than that of an aqueous system [65]. Alkaline gel electrolytes (AGEs), consisting of low molecular
weight polymer and alkaline solutions have been developed to mitigate these issues for primary
lithium–air batteries [66].
Ionic liquid electrolyte: Ionic liquids are non-aqueous liquid electrolytes, including two types of
cations: large organic cations with organic/inorganic anions and alkali metal ions in an organic solvent,
such as organic carbonates, ethers, and esters [67,68]. Lithium salt, such as LiPF6 , LiAsF6 , LiN(SO2 CF3 )2 ,
and LiSO3 CF3 are commonly used in LABs [69]. PYR14TFSI–TEGDME–LiCF3 SO3 are also employed
in LABs [70], consisting of LiCF3 SO3 in tetraethylene glycol dimethyl ether (TEGDME) and pure
PYR14TFSI. Ionic liquid electrolytes also face challenges because of the formation of carbonates,
which consume the electrolyte and block the electrode pores. What is more, the understanding of
the oxygen reaction in an ionic liquid is very limited. These hinder the practical application of ionic
liquid electrolytes.
In summary, neutral salt solution, acidic solutions, and hybrid electrolyte are rarely used in
industrial application. Alkaline solutions electrolytes and ionic liquid electrolyte are usually employed.
Aqueous electrolytes do not match LABs. Furthermore, solid-state electrolytes can work in all MABs.
5. Advanced Manufacturing of MABs

Advanced manufacturing techniques for electrodes and batteries is composed of printing and
laser processing. Printing technology has various advantages in microstructure controlling and large
batch low-cost fabrication. Printing includes screen printing [71], spray printing [72], direct ink writing
processing [73], and roll-to-roll fabrication, as shown in Figure 15. Figure 16 shows printed 1- to 4D
structures. 3D and 4D printing are achieved by layer-to-layer printing of functional micro/nanomaterials
in geometric and
Appl. Sci. 2019, 9, xtemporal complexes.
FOR PEER REVIEW 15 of 22
Figure
Figure 15.15. Schematics
Schematics ofof
(a)(a)a ascreen
screenprinting
printing[71] (Copyright ©
2017,RSC
RSCPub),
Pub),(b)
(b)spray
sprayprinting
printing[72]
[72]
(Copyright © 2015, John Wiley and Sons), (c) direct ink writing processes [73] (Copyright
(Copyright © 2015, John Wiley and Sons), (c) direct ink writing processes [73] (Copyright © 2017, © 2017, John
Wiley
John and
Wiley Sons).
and Sons).
Appl. Sci. 2019, 9, 2787 15 of 22
Screen printing is one popular and simple method among printing technologies. During screen
printing, the ink is pressed through a patterned screen onto the substrate using a roller and forms a film
with the structures defined by the patterned screen. Spray printing injects particles from a solution
andFigure
can easily fabricate large area sheets with a non-contact mode. Meanwhile, direct ink writing
15. Schematics of (a) a screen printing [71] (Copyright © 2017, RSC Pub), (b) spray printing [72]
using a nozzle can feasibly
(Copyright © 2015, form and
John Wiley a 2D–3D
Sons),structure with
(c) direct ink a certain
writing thickness
processes on the substrate.
[73] (Copyright Therefore,
© 2017, John
different
Wileyprinting technologies can be applied to various battery electrodes.
and Sons).
Figure 16. Of 1-, 2-, 3-, and 4D concepts. A 4D structure is a structure (x, y, z) made by 3D changes over
time (t).
Figure 16.Arrows indicate
of 1-, 2-, 3-, andthe
4Ddirection
concepts.ofAchange with respect
4D structure to time. (x, y, z) made by 3D changes
is a structure
over time (t). Arrows indicate the direction of change with respect to time.
5.1. Spray Coating and 2D Printing
5.1. Spray Coating
Spray and
coating is 2D Printing coating method to fabricate composites by depositing particles onto
a traditional
the Spray
substrate surface.
coating Accordingcoating
is a traditional to the method
workingtomechanism, spray canbybe
fabricate composites divided into
depositing two types,
particles onto
cold spray and thermal spray. Thermal spray delivers melted metal drops or
the substrate surface. According to the working mechanism, spray can be divided into two types,non-metal particles at high
temperatures
cold spray andand formsspray.
thermal a coatThermal
on the substrate [74]. Thermal
spray delivers spray drops
melted metal has relatively wide applications
or non-metal particles at
in metal or alloy materials processing, such as surface coating and
high temperatures and forms a coat on the substrate [74]. Thermal spray has relatively corrosion resistance. In contrast
wide
to thermal spray,
applications in metal cold spraymaterials
or alloy without heating
processing,is a such
coating processcoating
as surface to accelerate particlesresistance.
and corrosion using the
Insupersonic
contrast todriving
thermal gasspray,
passing through
cold spray awithout
convergent–divergent nozzleprocess
heating is a coating and subsequently
to accelerate ejected onto
particles
a substrate in high speed [75]. Cold spray enables the delivery of various
using the supersonic driving gas passing through a convergent–divergent nozzle and subsequentlymaterials, including high
meltingonto
ejected pointa metal materials,
substrate in highlow melting
speed [75].point
Coldpolymer materials,
spray enables theeven biomaterials.
delivery of various Helfritch [76]
materials,
reviewed 24 new applications of cold spray, such as medical devices,
including high melting point metal materials, low melting point polymer materials, even electronics, microdevices, and
so on.
biomaterials. Helfritch [76] reviewed 24 new applications of cold spray, such as medical devices,
Printing is another advanced
electronics, microdevices, and so on. manufacturing method, including inkjet printing, lithography,
3D printing, 4D printing.
Printing is another advanced In thismanufacturing
section, we will first discuss
method, lithography
including and inkjet
inkjet printing, 2D printing.
lithography, 3D
Inkjet printing
printing, [77,78]In
4D printing. is this
additive manufacturing
section, we will first and appears
discuss after screen-printing
lithography and inkjet 2Dand spin coating.
printing. Inkjet
The principle
printing [77,78]ofisinkjet printing
additive consists ofand
manufacturing five appears
stages: drop
after ejection, drop flight,
screen-printing and drop impact, drop
spin coating. The
spreading, and drop solidification. Inkjet printing has been used in depositing
principle of inkjet printing consists of five stages: drop ejection, drop flight, drop impact, functional inksdrop
onto
various substrates
spreading, and dropfor numerical devices,
solidification. to specific,
Inkjet printing sensors,
has been usedmicro-batteries, solar cell, inks
in depositing functional and onto
other
conductive parts of cells [79–82]. Lim [83] thoroughly reviewed technology issues
various substrates for numerical devices, to specific, sensors, micro-batteries, solar cell, and other and influence on
different substrates for printed capacitive sensors. Furthermore, since Mirkin [84] reported “Dip-pen
nanolithography” (DPN) in science, lithography became the focus of contemporary microfabrication.
A DPN system is composed of an atomic force microscope tip as a “nib”, solid-state substrate as “paper”,
and molecules with a chemical affinity for the solid-state substrate “ink”. By controlling the AFM
tip, the nib directly writes controlled patterns on the substrate materials. Lithography contributes to
microfabrication in nanomaterials and micro-devices, such as micro-reactors and sensors, micro-optical
system [85–88]. Shao [89] reported nanoimprint lithography in the processing of flexible electronics,
conductive electrodes, optoelectronic devices, flexible microlens, and flexible sensors. Certainly, it is
feasible to print electrodes with a thin-film structure for metal–air batteries.
AFM tip, the nib directly writes controlled patterns on the substrate materials. Lithography
contributes to microfabrication in nanomaterials and micro-devices, such as micro-reactors and
sensors, micro-optical system [85–88]. Shao [89] reported nanoimprint lithography in the processing
of flexible electronics, conductive electrodes, optoelectronic devices, flexible microlens, and flexible
sensors. Certainly, it is feasible to print electrodes with a thin-film structure for metal–air batteries.
Appl. Sci. 2019, 9, 2787 16 of 22
5.2. Laser Processing

5.2. Laser Processing
Laser processing has gained more and more attention in recent years. Laser ablation, laser
cutting,
Laser laser welding,
processing laser
has sintering,
gained more andlasermore
direct writing,
attention inand other
recent laser-assisted
years. synthesis
Laser ablation, process
laser cutting,
are powerful
laser toolssintering,
welding, laser for precise manufacturing
laser direct writing,[90,91].
and otherForlaser-assisted
microfabrication, laser
synthesis ablation
process are is used to
powerful
fabricate porous graphene and graphene quantum dots. Laser power, spot
tools for precise manufacturing [90,91]. For microfabrication, laser ablation is used to fabricate porous size diameter, hatch
distance, and
graphene scanning
graphene speed, wavelength,
quantum dots. Laserhadpower,
an influence
spot sizeon the formation
diameter, of nanomaterials
hatch distance, and
scanning speed,
nanostructures
wavelength, [92,93].
had an Lasers
influence on thecanformation
be applied for sintering and
of nanomaterials various materials [92,93].
nanostructures including metals,
Lasers can
ceramics,
be appliedand polymersvarious
for sintering [94–96].materials
In recentincluding
years, laser processing
metals, has been
ceramics, employed[94–96].
and polymers in the fabrication
In recent
of electrodes
years, [97], supercapacitors
laser processing has been employed [98,99],ineven full batteries
the fabrication [100]. Successful
of electrodes micromanufacturing
[97], supercapacitors [98,99],
includes
even laser-drilling
full batteries [100].ofSuccessful
microholes in LiFePO4 cathode
micromanufacturing for Li-ion
includes batteriesof[101]
laser-drilling and laser
microholes in
LiFePO 4 cathode
carbonization for Li-ion
anode batteries
(graphene) [101]
for an and laserfilm
interdigital carbonization
battery [102]. anode (graphene)
Li [6] for an interdigital
reported femtosecond laser-
film battery
reduced nano[102]. Li [6]
joined reportedoxide/Au
graphene femtosecond laser-reduced
conductive network nano joined graphene oxide/Au
as micro-supercapacitors conductive
electrodes. Pröll
network as micro-supercapacitors
[103] reported electrodes.
femtosecond-laser structuring ofPröll
LiMn[103] reported cathodes
2O4 composite femtosecond-laser structuring of
for Li-ion micro-batteries.
LiMnYu 2 O4[3]
composite
reportedcathodes for Li-ion
laser sintering micro-batteries.
of printed anodes for AABs. Results indicated that laser sintering
Yu [3] reported
can remove the organiclasersolvent
sinteringfrom of the
printed
printedanodes for AABs. Results
Al nanoparticle indicated
slurry and thatthe
increase laser sintering
conductivity
can remove
of the the organic
printed anode. solvent from the printed
Electrochemical Al nanoparticle
characterization slurry andlaser
demonstrated increase
power the conductivity
of 10 W for
of the printed
sintering anode.performance,
for better Electrochemical andcharacterization
3-layer printeddemonstrated
anode with alaser biggerpower of 10 Wcapacity.
discharge for sintering
A 3-
for better performance, and 3-layer printed anode with a bigger discharge
layer battery cell can yield a 239 mAh g discharge capacity at an operation voltage of 0.95 V, as
−1 capacity. A 3-layer battery
cell can yield
shown mAh g−1 discharge capacity at an operation voltage of 0.95 V, as shown in Figure 17.
a 23917.
in Figure
Figure 17. (a)

Figure17. (a) Schematic
Schematicof ofaluminum–air
aluminum–airbatteries
batteries(AAB)
(AAB)working
workingprinciple,
principle,(b)
(b)Photo
Photoofofaapackaged
packaged
battery
batterycell,
cell,(c)
(c)The
Thefirst
firstcycle
cycledischarge
dischargecapacity
capacitywith
withdifferent
differentlaser
lasersintering
sinteringpowers.
powers.(d)
(d)Discharge
Discharge
capacity
capacityfor
for3D3Dprinted
printedanode
anodeand
andrelationship between
relationship betweenanode
anodethickness
thicknessand
andcapacity [3][3]
capacity (Copyright ©
(Copyright
2018, Electrochemical Society).
© 2018, Electrochemical Society).
5.3. 3D Printing
Traditional thin film 2D batteries have suffered from limited energy capacity. 3D printing of
flexible micro-batteries with nanostructures can overcome this weakness. Currently, the printed parts of
batteries can be electrodes, current collector, solid-state separator, and catalyst in metal–air batteries [104].
Zhou [105] reviewed 3D printing energy storage devices with a sandwich-type and in-plane architecture
and demonstrated that the electrochemical energy storage systems can be greatly promoted with 3D
printing. Lewis et al. [106,107] reported 3D fully printed electrodes for Li-ion batteries. Li4 Ti5 O12 (LTO)
and LiFePO4 (LFP) were separately employed as anode and cathode materials. Electrode material
inks were printed onto the substrate, forming multilayer electrodes and an anode and cathode in an
interdigitated structure. The results showed that the charge and discharge of 8-layer full cell delivered
Appl. Sci. 2019, 9, 2787 17 of 22
1.2 mAh cm−2 at a rate of 0.5 C. EIS test revealed the thicker electrode had higher resistance. Meanwhile,
CV testing showed the thin wall displayed broader redox peaks. Furthermore, both thin and thick
electrodes exhibit excellent Coulombic efficiencies. 3D printed LIBs had 4.45 mAh cm−2 at 0.14 mA cm−2 ,
corresponding a full cell delivering 14.5 mAh cm−2 at 0.2 mA cm−2 . The same printed technology can
also be employed for MABs. For MABs, screen printing has been used in catalysts [108]. A remarkable
shortcoming is the narrow choice of suitable materials for printing. In addition, expensive equipment
also limits application. However, 3D printing is the destructive technology in MAB manufacturing due
to unprecedented designing freedom, high precision, and cost-effective processing.
6. Summary and Outlook

In summary, this paper briefly reviewed the recent advances in the studies of the metal–air
batteries. Better batteries should be an excellent combination of cathode, anode, and electrolyte.,
however, there are still some problems to be solved, such as anode side reaction, impure gas CO2
release, electrolyte instability, and so on.
Essentially, improving ORR and OER are quite important to the cathode. Crystallographic
structure, materials size, materials morphology, carbon-based materials-doped, and composites can
influence different activities of catalyst, which is required to improve both ORR and OER in the cathode.
Nanocomposites and doped-carbon materials are good choices for catalysts in ORR and OER.
Research indicates that compared with traditional alloy as an anode, alloys with nanocomposites can
reduce the side reaction and improve discharge capacity. While various electrolytes have different
advantages more efficient solid-state electrolyte is required in rechargeable metal–air batteries.
Integration of advanced manufacturing, especially 3D printing and laser processing, opens
new horizons for MABs. These manufacturing processes allow a better strategy for the systematic
combination of the best performance of anodes, cathodes, and electrolyte for improved energy density,
efficiency, and cycling stabilities. Although many issues still exist, the further development of MABs,
as a compelling alternative to LIBs, holds great promise to address emergent needs of portable
electronics, electrical vehicles, and IoTs.
Author Contributions: C.W. is responsible for the reference survey, analysis, figure preparation and manuscript drafting.
Y.Y. contributes to the laser processing section. J.N., X.L., Y.Z. contribute to the section of “in situ characterization using an
electron microscope”. Y.L., D.B., J.P. are responsible for the revision of the paper. A.H. advises the review structures,
revises the logic order of the chapters and polishes the final manuscript.
Funding: This work is partially supported by the National Natural Science Foundation of China (51575016) and
NSFC-DFG joint project (51761135129).
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Gür, T.M. Review of electrical energy storage technologies, materials and systems: Challenges and prospects
for large-scale grid storage. Energy Environ. Sci. 2018, 11, 2696–2767. [CrossRef]
2. Li, S.; Guo, Z.P.; Wang, C.Y.; Wallace, G.G.; Liu, H.K. Flexible cellulose based polypyrrole–multiwalled
carbon nanotube films for bio-compatible zinc batteries activated by simulated body fluids. J. Mater. Chem.
A 2013, 1, 14300–14305. [CrossRef]
3. Yu, Y.; Chen, M.; Wang, S.; Hill, C.; Joshi, P.; Kuruganti, T.; Hu, A. Laser sintering of printed anodes for al-air
batteries. J. Electrochem. Soc. 2018, 165, A584–A592. [CrossRef]
4. Jeżowski, P.; Crosnier, O.; Deunf, E.; Poizot, P.; Béguin, F.; Brousse, T. Safe and recyclable lithium-ion
capacitors using sacrificial organic lithium salt. Nat. Mater. 2018, 17, 167. [CrossRef] [PubMed]
5. Jeżowski, P.; Fic, K.; Crosnier, O.; Broussebc, T.; Béguin, F. Lithium rhenium (vii) oxide as a novel material for
graphite pre-lithiation in high performance lithium-ion capacitors. J. Mater. Chem. A 2016, 4, 12609–12615.
[CrossRef]
Appl. Sci. 2019, 9, 2787 18 of 22
6. Li, R.-Z.; Peng, R.; Kihm, K.D.; Bai, S.; Bridges, D.; Tumuluri, U.; Wu, Z.; Zhang, T.; Compagnini, G.;
Feng, Z. High-rate in-plane micro-supercapacitors scribed onto photo paper using in situ femtolaser-reduced
graphene oxide/Au nanoparticle microelectrodes. Energy Environ. Sci. 2016, 9, 1458–1467.
7. Jeżowski, P.; Fic, K.; Crosnier, O.; Brousse, T.; Béguin, F. Use of sacrificial lithium nickel oxide for loading
graphitic anode in Li-ion capacitors. Electrochim. Acta 2016, 206, 440–445.
8. Pellow, M.A.; Emmott CJ, M.; Barnhart, C.J.; Benson, S.M. Hydrogen or batteries for grid storage? A net
energy analysis. Energy Environ. Sci. 2015, 8, 1938–1952. [CrossRef]
9. Zhang, X.; Wang, X.G.; Xie, Z.; Zhou, Z. Recent progress in rechargeable alkali metal–air batteries. Green
Energy Environ. 2016, 1, 4–17. [CrossRef]
10. McKerracher, R.D.; Ponce de Leon, C.; Wills RG, A.; Shah, D.A.A.; Walsh, P.F.C. A review of the iron–air
secondary battery for energy storage. ChemPlusChem 2015, 80, 323–335. [CrossRef]
11. Zhang, Z.; Zuo, C.; Liu, Z.; Yu, Y.; Zuo, Y.; Song, Y. All-solid-state Al–air batteries with polymer alkaline gel
electrolyte. J. Power Sources 2014, 251, 470–475. [CrossRef]
12. Li, Y.; Dai, H. Recent advances in zinc–air batteries. Chem. Soc. Rev. 2014, 43, 5257–5275. [CrossRef]
[PubMed]
13. Wang, Y.; Kwok, H.; Pan, W.; Zhang, H.; Leung, D.Y.C. Innovative paper-based Al-air batteries as a low-cost
and green energy technology for the miniwatt market. J. Power Sources 2019, 414, 278–282. [CrossRef]
14. Wu, D.; Guo, Z.; Yin, X.; Pang, Q.; Tu, B.; Zhang, L.; Wang, Y.; Li, Q. Metal–organic frameworks as cathode
materials for Li–O2 batteries. Adv. Mater. 2014, 26, 3258–3262. [CrossRef] [PubMed]
15. Cheng, F.; Chen, J. Metal–air batteries: From oxygen reduction electrochemistry to cathode catalysts. Chem.
Soc. Rev. 2012, 41, 2172–2192. [CrossRef] [PubMed]
16. Cheng, J.; Zhang, L.; Yang, Y.S.; Wen, Y.-H.; Cao, G.-P.; Wang, X.-D. Preliminary study of single flow
zinc–nickel battery. Electrochem. Commun. 2007, 9, 2639–2642. [CrossRef]
17. Fu, J.; Zhang, J.; Song, X.; Zarrin, H.; Tian, X.; Qiao, J.; Rasen, L.; Li, K.; Chen, Z. A flexible solid-state
electrolyte for wide-scale integration of rechargeable zinc–air batteries. Energy Environ. Sci. 2016, 9, 663–670.
[CrossRef]
18. Zhou, G.; Li, F.; Cheng, H.M. Progress in flexible lithium batteries and future prospects. Energy Environ. Sci.
2014, 7, 1307–1338. [CrossRef]
19. Sumboja, A.; Ge, X.; Zong, Y.; Liu, Z.P. Rogress in development of flexible metal–air batteries. Funct. Mater.
Lett. 2016, 9, 1630001. [CrossRef]
20. Gu, P.; Zheng, M.; Zhao, Q.; Xiao, X.; Xuea, H.; Pang, H. Rechargeable zinc–air batteries: A promising way to
green energy. J. Mater. Chem. A 2017, 5, 7651–7666. [CrossRef]
21. Guo, S.; Zhang, S.; Sun, S. Tuning nanoparticle catalysis for the oxygen reduction reaction. Ang. Chem. Int.
Edit. 2013, 52, 8526–8544. [CrossRef] [PubMed]
22. Jörissen, L. Bifunctional oxygen/air electrodes. J. Power Sources 2006, 155, 23–32. [CrossRef]
23. Cao, R.; Lee, J.S.; Liu, M.; Cho, J. Recent progress in non-precious catalysts for metal-air batteries. Adv.
Energy Mater. 2012, 2, 816–829. [CrossRef]
24. Qian, L.; Lu, Z.; Xu, T.; Wu, X.; Tian, Y.; Li, Y.; Huo, Z.; Sun, X.; Duan, X. Trinary layered double hydroxides
as high-performance bifunctional materials for oxygen electrocatalysis. Adv. Energy Mater. 2015, 5, 1500245.
[CrossRef]
25. Liu, Y.; Cao, L.J.; Cao, C.W.; Wang, M.; Leung, K.-L.; Zeng, S.-S.; Hung, T.F.; Chung, C.Y.; Lu, Z.-G. Facile
synthesis of spinel CuCo2 O4 nanocrystals as high-performance cathode catalysts for rechargeable Li–air
batteries. Chem. Commun. 2014, 50, 14635–14638. [CrossRef]
26. Han, X.; Wu, X.; Zhong, C.; Deng, Y.; Zhao, N.; Hu, W. NiCo2 S4 nanocrystals anchored on nitrogen-doped
carbon nanotubes as a highly efficient bifunctional electrocatalyst for rechargeable zinc-air batteries. Nano
Energy 2017, 31, 541–550. [CrossRef]
27. Dresp, S.; Luo, F.; Schmack, R.; Kühl, S.; Gliecha, M.; Strasser, P. An efficient bifunctional two-component
catalyst for oxygen reduction and oxygen evolution in reversible fuel cells, electrolyzers and rechargeable air
electrodes. Energy Environ. Sci. 2016, 9, 2020–2024. [CrossRef]
28. Indra, A.; Menezes, P.W.; Sahraie, N.R.; Bergmann, A.; Das, C.; Tallarida, M.; Schmeißer, D.; Strasser, P.;
Driess, M. Unification of catalytic water oxidation and oxygen reduction reactions: Amorphous beat
crystalline cobalt iron oxides. J. Am. Chem. Soc. 2014, 136, 17530–17536. [CrossRef]
Appl. Sci. 2019, 9, 2787 19 of 22
29. Yamada, I.; Fujii, H.; Takamatsu, A.; Ikeno, H.; Wada, K.; Tsukasaki, H.; Kawaguchi, S.; Mori, S.; Yagi, S.
Bifunctional oxygen reaction catalysis of quadruple manganese Perovskites. Adv. Mater. 2017, 29, 1603004.
[CrossRef]
30. Maiyalagan, T.; Jarvis, K.A.; Therese, S.; Ferreira, P.J.; Manthiram, A. Spinel-type lithium cobalt oxide as a
bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions. Nat. Commun. 2014, 5,
3949. [CrossRef]
31. Gummow, R.J.; Thackeray, M.M.; David, W.I.F.; Hull, S. Structure and electrochemistry of lithium cobalt
oxide synthesised at 400 ◦ C. Mater. Res. Bull. 1992, 27, 327–337. [CrossRef]
32. Gummow, R.J.; Liles, D.C.; Thackeray, M.M. Spinel versus layered structures for lithium cobalt oxide
synthesised at 400 ◦ C. Mater. Res. Bull. 1993, 28, 235–246. [CrossRef]
33. Lang, X.; Ge, F.; Cai, K.; Lan Li Wang, Q.; Zhang, Q. A novel Mn3 O4 /MnO nano spherical transition metal
compound prepared by vacuum direct current arc method as bi-functional catalyst for lithium-oxygen
battery with excellent electrochemical performances. J. Alloy. Compd. 2019, 770, 451–457. [CrossRef]
34. Shin, B.; Choi, S.; Tak, Y. Electrocatalytic activity of Co-based perovskite oxides for oxygen reduction and
evolution reactions]. Int. J. Electrochem. Sci. 2016, 11, 5900. [CrossRef]
35. Park, M.G.; Lee, D.U.; Seo, M.H.; Cano, Z.P.; Chen, Z. 3D ordered mesoporous bifunctional oxygen catalyst
for electrically rechargeable zinc–air batteries. Small 2016, 12, 2707–2714. [CrossRef] [PubMed]
36. Tian, Y.; Xu, L.; Bao, J.; Qian, J.; Su, H.; Li, H.; Gu, H.; Yan, C.; Li, H. Hollow cobalt oxide nanoparticles
embedded in nitrogen-doped carbon nanosheets as an efficient bifunctional catalyst for Zn–air battery.
J. Energy Chem. 2019, 33, 59–66. [CrossRef]
37. Osgood, H.; Devaguptapu, S.V.; Xu, H.; Cho, J.; Wu, G. Transition metal (Fe, Co, Ni, and Mn) oxides for
oxygen reduction and evolution bifunctional catalysts in alkaline media. Nano Today 2016, 11, 601–625.
[CrossRef]
38. Zhang, Y.; Jiang, W.J.; Guo, L.; Zhang, X.; Hu, J.-S.; Wei, Z.; Wan, L.-J. Confining iron carbide nanocrystals
inside CNx @ CNT toward an efficient electrocatalyst for oxygen reduction reaction. ACS Appl. Mater. Inter.
2015, 7, 11508–11515. [CrossRef]
39. Wu, G.; Santandreu, A.; Kellogg, W.; Gupta, S.; Ogoke, O.; Zhang, H.; Wang, H.-L.; Dai, L. Carbon
nanocomposite catalysts for oxygen reduction and evolution reactions: From nitrogen doping to
transition-metal addition. Nano Energy 2016, 29, 83–110. [CrossRef]
40. Wang, L.; Liang, K.; Deng, L.; Liu, Y.-N. Protein hydrogel networks: A unique approach to heteroatom
self-doped hierarchically porous carbon structures as an efficient ORR electrocatalyst in both basic and acidic
conditions. Appl. Catal. B Environ. 2019, 246, 89–99. [CrossRef]
41. Zhou, N.; Wang, N.; Wu, Z.; Li, L. Probing Active Sites on Metal-Free, Nitrogen-Doped Carbons for Oxygen
Electroreduction: A Review. Catalysts 2018, 8, 509. [CrossRef]
42. Xu, Y.F.; Chen, Y.; Xu, G.L.; Zhang, X.-R.; Chen, Z.; Li, J.-T.; Huang, L.; Amine, K.; Sun, S.-G. RuO2
nanoparticles supported on MnO2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen
battery. Nano Energy 2016, 28, 63–70. [CrossRef]
43. Harrison, K.L.; Zavadil, K.R.; Hahn, N.T.; Meng, X.; Elam, J.W.; Leenheer, A.; Zhang, J.-G.; Jungjohann, K.L.
Lithium self-discharge and its prevention: Direct visualization through in situ electrochemical scanning
transmission electron microscopy. ACS Nano 2017, 11, 11194–11205. [CrossRef] [PubMed]
44. Yoon, I.; Jurng, S.; Abraham, D.P.; Lucht, B.L.; Guduru, P.R. In Situ Measurement of the Plane-Strain Modulus
of the Solid Electrolyte Interphase on Lithium-Metal Anodes in Ionic Liquid Electrolytes. Nano Lett. 2018, 18,
5752–5759. [CrossRef] [PubMed]
45. Li, Y.; Sun, H.; Cheng, X.; Zhang, Y.; Zhao, K. In-situ TEM experiments and first-principles studies on the
electrochemical and mechanical behaviors of α-MoO3 in Li-ion batteries. Nano Energy 2016, 27, 95–102.
[CrossRef]
46. Liu, Q.; Geng, L.; Yang, T.; Tang, Y.; Jia, P.; Li, Y.; Li, H.; Shen, T.; Zhang, L.; Huang, J. In-situ imaging
electrocatalysis in a Na-O2 battery with Au-coated MnO2 nanowires air cathode. Energy Storage Mater. 2019,
19, 48–55. [CrossRef]
47. Liu, Q.; Yang, T.; Du, C.; Tang, Y.; Sun, Y.; Jia, P.; Chen, J.; Ye, H.; Shen, T.; Peng, Q.; et al. In Situ Imaging the
Oxygen Reduction Reactions of Solid State Na–O2 Batteries with CuO Nanowires as the Air Cathode. Nano
Lett. 2018, 18, 3723–3730. [CrossRef] [PubMed]
Appl. Sci. 2019, 9, 2787 20 of 22
48. Liu, C.; Ye, S. In situ atomic force microscopy (AFM) study of oxygen reduction reaction on a gold electrode
surface in a dimethyl sulfoxide (DMSO)-Based electrolyte solution. J. Phys. Chem. C 2016, 120, 25246–25255.
[CrossRef]
49. Fan, L.; Lu, H.; Leng, J.; Sun, Z.; Chen, C. The study of industrial aluminum alloy as anodes for aluminum-air
batteries in alkaline electrolytes. J. Electrochem. Soc. 2016, 163, A8–A12. [CrossRef]
50. Cho, Y.J.; Park, I.J.; Lee, H.J.; Kim, J.-G. Aluminum anode for aluminum–air battery–Part I: Influence of
aluminum purity. J. Power Sources 2015, 277, 370–378. [CrossRef]
51. Park, I.J.; Choi, S.R.; Kim, J.G. Aluminum anode for aluminum-air battery–Part II: Influence of In addition
on the electrochemical characteristics of Al-Zn alloy in alkaline solution. J. Power Sources 2017, 357, 47–55.
[CrossRef]
52. Lan, C.J.; Chin, T.S.; Lin, P.H.; Perng, T.P. Zn-Al alloy as a new anode-metal of a zinc-air battery. J. New Mater.
Electrochem. Syst 2006, 9, 27–32.
53. Mutlu, R.N. Copper-deposited aluminum anode for aluminum-air battery. J. Solid State Electrochem. 2019, 23,
529–541. [CrossRef]
54. Hang, B.T.; Watanabe, T.; Egashira, M.; Watanabe, I.; Okada, S.; Yamaki, J.-I. The effect of additives on the
electrochemical properties of Fe/C composite for Fe/air battery anode. J. Power Sources 2006, 155, 461–469.
[CrossRef]
55. Lee, C.W.; Eom, S.W.; Sathiyanarayanan, K.; SooYun, M. Preliminary comparative studies of zinc and zinc
oxide electrodes on corrosion reaction and reversible reaction for zinc/air fuel cells. Electrochim. Acta 2006,
52, 1588–1591. [CrossRef]
56. Zhao, Y.; VanderNoot, T.J. Electrodeposition of aluminium from room temperature AlCl3 -TMPAC molten
salts. Electrochim. Acta 1997, 42, 1639–1643. [CrossRef]
57. Zhao, X.; Xu, N.; Li, X.; Huang, K. Energy storage characteristics of a new rechargeable solid oxide iron–air
battery. RSC Adv. 2012, 2, 10163. [CrossRef]
58. Ponrouch, A.; Frontera, C.; Bardé, F.; Palacín, M.R. Towards a calcium-based rechargeable battery. Nat. Mater.
2016, 15, 169. [CrossRef]
59. Lee, S.M.; Kim, Y.J.; Eom, S.W.; Choi, N.-S.; Kim, K.-W.; Cho, S.-B. Improvement in self-discharge of Zn
anode by applying surface modification for Zn–air batteries with high energy density. J. Power Sources 2013,
227, 177–184. [CrossRef]
60. Stark, J.K.; Ding, Y.; Kohl, P.A. Dendrite-free electrodeposition and reoxidation of lithium-sodium alloy for
metal-anode battery. J. Electrochem. Soc. 2011, 158, A1100–A1105. [CrossRef]
61. Yoon, S.; Lee, J.; Kim, S.O.; Sohn, H.-J. Enhanced cyclability and surface characteristics of lithium batteries by
Li–Mg co-deposition and addition of HF acid in electrolyte. Electrochim. Acta 2008, 53, 2501–2506. [CrossRef]
62. Ishikawa, M.; Machino, S.; Morita, M. Electrochemical control of a Li metal anode interface: Improvement of
Li cyclability by inorganic additives compatible with electrolytes. J. Electroanal. Chem. 1999, 473, 279–284.
[CrossRef]
63. Smoljko, I.; Gudić, S.; Kuzmanić, N.; Kliškić, M. Electrochemical properties of aluminium anodes for Al/air
batteries with aqueous sodium chloride electrolyte. J. Appl. Electrochem. 2012, 42, 969–977. [CrossRef]
64. Yu, X.; Manthiram, A. A Voltage-Enhanced, Low-Cost Aqueous Iron–Air Battery Enabled with a Mediator-Ion
Solid Electrolyte. ACS Energy Lett. 2017, 2, 1050–1055. [CrossRef]
65. Wang, Y.J.; Qiao, J.; Baker, R.; Zhang, J. Alkaline polymer electrolyte membranes for fuel cell applications.
Chem. Soc. Rev. 2013, 42, 5768–5787. [CrossRef]
66. Li, F.; Kitaura, H.; Zhou, H. The pursuit of rechargeable solid-state Li–air batteries. Energy Environ. Sci. 2013,
6, 2302–2311. [CrossRef]
67. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 2004, 104,
4303–4418. [CrossRef]
68. Mokhtar, M.; MeorTalib, M.Z.; Majlan, E.H.; Tasirin, S.M.; Ramli, W.M.F.W.; Daud, W.R.W.; Sahari, J. Recent
developments in materials for aluminum–air batteries: A review. J. Ind. Eng. Chem. 2015, 32, 1–20. [CrossRef]
69. Daming, G.; Yu, W.; Shuo, G.; Zhang, C. Research Progress and Optimization of Non-aqueous Electrolyte for
Lithium Air Batteries. ACTA Chim. Sin. 2013, 71, 1354–1364.
70. Cecchetto, L.; Salomon, M.; Scrosati, B.; Croce, F. Study of a Li–air battery having an electrolyte solution
formed by a mixture of an ether-based aprotic solvent and an ionic liquid. J. Power Sources 2012, 213, 233–238.
[CrossRef]
Appl. Sci. 2019, 9, 2787 21 of 22
71. Shaheen, S.E.; Radspinner, R.; Peyghambarian, N.; Jabbour, G.E. Fabrication of bulk heterojunction plastic
solar cells by screen printing. Appl. Phys. Lett. 2001, 79, 2996–2998. [CrossRef]
72. Gan, J.A.; Berndt, C.C. Nanocomposite coatings: Thermal spray processing, microstructure and performance.
Int. Mater. Rev. 2015, 60, 195–244. [CrossRef]
73. Yin, S.; Chen, C.; Suo, X.; Lupoi, R. Cold-Sprayed Metal Coatings with Nanostructure. Adv. Mater. Sci. Eng.
2018, 2018, 2804576. [CrossRef]
74. Champagne, V.K.; Helfritch, D.J. Mainstreaming cold spray–push for applications. Surf. Eng. 2014, 30,
75. Cummins, G.; Desmulliez, M.P.Y. Inkjet printing of conductive materials: A review. Circuit World 2012, 38,
76. Li, R.Z.; Hu, A.; Zhang, T.; Oakes, K.D. Direct writing on paper of foldable capacitive touch pads with silver
nanowire inks. ACS Appl. Mater. Interfaces 2014, 6, 21721–21729. [CrossRef] [PubMed]
77. Sousa, R.E.; Costa, C.M.; Lanceros-Méndez, S. Advances and Future Challenges in Printed Batteries.
ChemSusChem 2015, 8, 3539–3555. [CrossRef]
78. Kim, H.J.; Kim, J.J.; Lee, J.K. Enhancement of the Surface Roughness by Powder Spray Coating on Zirconia
Substrate. J. Nanosci. Nanotechnol. 2019, 19, 6285–6290. [CrossRef]
79. Bonetti, I.; da Costa, C.E.; Paredes, R.S.C.; Paredes, R.S.C.; Sucharski, G.B.; da Costa, E.M.; Franco, E.;
Milan, J.C.G. Effect of flame spray deposition parameters on the microstructure, microhardness and corrosion
resistance of FeNbC coatings on AISI 1020 steel. Mater. Res. Express 2019, 6, 086530. [CrossRef]
80. Lotya, M.; Hernandez, Y.; King, P.J.; Smith, R.J.; Nicolosi, V.; Karlsson, L.S.; Blighe, F.M.; De, S.; Wang, Z.;
McGovern, I.T. Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions.
J. Am. Chem. Soc. 2009, 131, 3611–3620. [CrossRef]
81. Salim, A.; Lim, S. Review of recent inkjet-printed capacitive tactile sensors. Sensors 2017, 17, 2593. [CrossRef]
[PubMed]
82. Piner, R.D.; Zhu, J.; Xu, F.; Hong, S.; Mirkin, C.A. “Dip-pen” nanolithography. Science 1999, 283, 661–663.
[CrossRef] [PubMed]
83. Kelly, K.L.; Coronado, E.; Zhao, L.L.; Schatz, G.C. The optical properties of metal nanoparticles: The influence
of size, shape, and dielectric environment. J. Phys. Chem. B 2003, 107, 668–677. [CrossRef]
84. Mottay, E.; Liu, X.; Zhang, H.; Mazur, E. Industrial applications of ultrafast laser processing. MRS Bull. 2016,
41, 984–992. [CrossRef]
85. Yu, Y.; Bai, S.; Wang, S.; Hu, A. Ultra-Short Pulsed Laser Manufacturing and Surface Processing of
Microdevices. Engineering 2018, 4, 779–786. [CrossRef]
86. Yu, Y.; Wang, S.; Ma, D.; Joshi, P.; Hu, A. Recent Progress on Laser Manufacturing of Microsize Energy
Devices on Flexible Substrates. JOM 2018, 70, 1816–1822. [CrossRef]
87. Shao, J.Y.; Chen, X.L.; Li, X.M.; Tian, H. Nanoimprint lithography for the manufacturing of flexible electronics.
Sci. China Technol. Sci. 2019, 62, 175–198. [CrossRef]
88. Hu, A.; Rybachuk, M.; Lu, Q.B.; Duley, W. Direct synthesis of sp-bonded carbon chains on graphite surface
by femtosecond laser irradiation. Appl. Phys. Lett. 2007, 91, 131906. [CrossRef]
89. Hu, A.; Li, R.; Bridges, D.; Zhou, W. Photonic nanomanufacturing of high performance energy devices on
flexible substrates. J. Laser Appl. 2016, 28, 022602. [CrossRef]
90. Hu, A.; Lu, Q.B.; Duley, W.W.; Rybachuk, M. Spectroscopic characterization of carbon chains in nanostructured
tetrahedral carbon films synthesized by femtosecond pulsed laser deposition. J. Chem. Phys. 2007, 126,
154705. [CrossRef]
91. Wang, S.; Yu, Y.; Li, R.; Feng, G.; Wu, Z.; Compagnini, G.; Gulino, A.; Feng, Z.; Hu, A. High-performance
stacked in-plane supercapacitors and supercapacitor array fabricated by femtosecond laser 3D direct writing
on polyimide sheets. Electrochim. Acta 2017, 241, 153–161. [CrossRef]
92. Li, R.-Z.; Hu, A.; Bridges, D.; Zhang, T.; Oakes, K.D.; Peng, R.; Tumuluri, U.; Wue, Z.; Feng, Z. Robust Ag
nanoplate ink for flexible electronics packaging. Nanoscale 2015, 7, 7368–7377. [CrossRef] [PubMed]
93. Peng, P.; Hu, A.; Zhou, Y. Laser sintering of silver nanoparticle thin films: Microstructure and optical
properties. Appl. Phys. A 2012, 108, 685–691. [CrossRef]
94. Ma, Y.; Li, H.; Bridges, D.; Peng, P.; Lawrie, B.; Feng, Z.; Hu, A. Zero-dimensional to three-dimensional
nanojoining: Current status and potential applications. RSC Adv. 2016, 6, 75916–75936. [CrossRef]
Appl. Sci. 2019, 9, 2787 22 of 22
95. Pfleging, W. A review of laser electrode processing for development and manufacturing of lithium-ion
batteries. Nanophotonics 2018, 7, 549–573. [CrossRef]
96. Gao, W.; Singh, N.; Song, L.; Liu, Z.; Reddy, A.L.M.; Ci, L.; Vajtai, R.; Zhang, Q.; Wei, B.; Ajayan, P.M. Direct
laser writing of micro-supercapacitors on hydrated graphite oxide films. Nat. Nanotechnol. 2011, 6, 496.
[CrossRef]
97. Ma, D.L.; Ma, Y.; Chen, Z.W.; Hu, A.M. A silk fabric derived carbon fibre net for transparent capacitive touch
pads and all-solid supercapacitors. J. Mater. Chem. A 2017, 5, 20608–20614. [CrossRef]
98. Ohta, S.; Komagata, S.; Seki, J.; Saeki, T.; Morishita, S.; Asaoka, T. All-solid-state lithium ion battery using
garnet-type oxide and Li3 BO3 solid electrolytes fabricated by screen-printing. J. Power Sources 2013, 238,
53–56. [CrossRef]
99. Tsuda, T.; Ando, N.; Nakamura, S.; Ishihara, Y.; Hayashi, N.; Soma, N.; Gunji, T.; Tanabe, T.; Ohsaka, T.;
Matsumoto, F. Improvement of high-rate discharging performance of LiFePO4 cathodes by forming
micrometer-sized through-holed electrode structures with a pico-second pulsed laser. Electrochim. Acta 2019,
296, 27–38. [CrossRef]
100. Fu, K.; Wang, Y.; Yan, C.; Yao, Y.; Chen, Y.; Dai, J.; Lacey, S.; Wang, Y.; Wan, J.; Li, T. Graphene oxide-based
electrode inks for 3D-printed lithium-ion batteries. Adv. Mater. 2016, 28, 2587–2594. [CrossRef]
101. Pröll, J.; Kim, H.; Piqué, A.; Seifert, H.J.; Pfleging, W. Laser-printing and femtosecond-laser structuring of
LiMn2 O4 composite cathodes for Li-ion microbatteries. J. Power Sources 2014, 255, 116–124. [CrossRef]
102. Ferrari, S.; Loveridge, M.; Beattie, S.D.; Jahn, M.; Dashwood, R.J.; Bhagat, R. Latest advances in the
manufacturing of 3D rechargeable lithium microbatteries. J. Power Sources 2015, 286, 25–46. [CrossRef]
103. Tian, X.; Jin, J.; Yuan, S.; Chua, C.K.; Tor, S.B.; Zhou, K. Emerging 3D-printed electrochemical energy storage
devices: A critical review. Adv. Energy Mater. 2017, 7, 1700127. [CrossRef]
104. Sun, K.; Wei, T.S.; Ahn, B.Y.; Seo, J.Y.; Dillon, S.J.; Lewis, J.A. 3D printing of interdigitated Li-Ion microbattery
architectures. Adv. Mater. 2013, 25, 4539–4543. [CrossRef]
105. Wei, T.S.; Ahn, B.Y.; Grotto, J.; Lewis, J.A. 3D Printing of Customized Li-Ion Batteries with Thick Electrodes.
Adv. Mater. 2018, 30, 1703027. [CrossRef]
106. Jung, C.Y.; Zhao, T.S.; An, L.; Wei, Z.H. Screen printed cathode for non-aqueous lithium–oxygen batteries.
J. Power Sources 2015, 297, 174–180. [CrossRef]
107. Zhao, C.; Wang, C.; Gorkin Iii, R.; Beirne, S.; Shu, K.; Wallace, G.G. Three dimensional (3D) printed electrodes
for interdigitated supercapacitors. Electrochem. Commun. 2014, 41, 20–23. [CrossRef]
108. Yang, Y.; Shi, M.; Zhou, Q.F.; Li, Y.-S.; Fu, Z.-W. Platinum nanoparticle–graphene hybrids synthesized by
liquid phase pulsed laser ablation as cathode catalysts for Li-air batteries. Electrochem. Commun. 2012, 20,
11–14. [CrossRef]
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Recent Progress of Metal-Air Batteries-A Mini Review-Aplicatii MAB PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Recent Progress of Metal-Air Batteries-A Mini Review-Aplicatii MAB PDF

Uploaded by

Copyright:

Available Formats

applied

Keywords: metal–air batteries; laser processing; 3D printing

1.1. Market Demand and Technical Tendencies

Appl. Sci. 2019, 9, 2787; doi:10.3390/app9142787 www.mdpi.com/journal/applsci

The reaction kinetics of FABsCathode:

Cathode: O2 + 2H2 O + 4e−

Overall reaction: 2O2 + 3Fe

Cathode: O2 + 2H2 O + 4e−

Overall reaction: 3O2 + 2Al

Cathode: O2 + 2H2 O + 4e−

1.3. Configuration of MABs

Appl. Sci. 2019, 9, x FOR PEER REVIEW

Appl. Sci. 2019, 9, x FOR PEER REVIEW 7 of 22

Figure 7.7. (a)

Appl. Sci. 2019, 9, x FOR PEER REVIEW 9 of 22

electrochemically generated TTF + through a homogeneous oxidation mechanism.

Figure 9.9. (a)

Ecorr (V vs. Hg/HgO) Icorr (mA cm−2 ) Rp (Ω cm2 )

3.2. Metal Coating and Composite Electrodes

Passivation layers: Passivation

4.1. Aqueous Electrolyte

Figure 14. (a)

4.2. Non-Aqueous Electrolyte

4.2. Non-Aqueous Electrolyte

5. Advanced Manufacturing of MABs

5.2. Laser Processing

Figure 17. (a)

6. Summary and Outlook

You might also like