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Metal Air Battery


Related terms:

Electrolyte, Electrocatalysts, Lithium, Electrode, Carbon Nanotubes, Graphene,


Cathode, Flux Density, Nitrogen, Oxide

Battery technologies
Farschad Torabi, Pouria Ahmadi, in Simulation of Battery Systems, 2020

1.4.5 Metal–air
Metal–air batteries are a mature family of primary and secondary cells. In metal–air
batteries the positive electrode is carbon–based covering with some precious metals
for reacting with oxygen. The other electrode is made of a metal such as zinc,
aluminum, magnesium, and lithium. Since in these batteries, the air is flowing
through the cell, they are sometimes categorized as fuel cells.
Among metal–air batteries, lithium–air has unique characteristics in concerning the
fact that its energy content is almost equal to diesel fossil fuel (see Table 1.5), in other
words, about 100 times the present conventional lithium–ion batteries. This fact
makes lithium–air attractive since by having a 50 kg battery pack, we can drive about
500 km with only one charge! That sounds very interesting.

At the present stage, lithium–air batteries with have been


demonstrated that its energy contents are five times the current conventional
lithium–polymer versions. However, their cyclic lives are low and cannot be
incorporated into electric cars.

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SECONDARY BATTERIES – METAL-AIR SYSTEMS |


Iron–Air (Secondary and Primary)
M. Egashira, in Encyclopedia of Electrochemical Power Sources, 2009

Overview
Iron–air battery is a type of metal–air battery that combines metallic negative
electrode having a low redox potential with air positive electrode. The basic
components of iron–air battery are iron negative electrode, air positive electrode, and
alkaline electrolyte. The theoretical voltage for this battery system is based on
Fe(II)/Fe(0) followed by Fe(III)/Fe(II) redox reaction at the negative electrode and the
oxygen reduction at the positive electrode is around 1.28 V. Therefore, the theoretical
specific energy is around 1000 Wh kg−1. Although the iron–air battery system has
these charge–discharge features and abundance of electrode material, it is a minor
candidate as a primary battery compared to zinc–air battery or aluminum–air battery
since both the expected capacity and the expected working voltage of iron negative
electrode are lower than those of zinc and aluminum. Moreover, as described in this

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article, the electrode reaction of iron is difficult in some ways compared to zinc.
Therefore, presently, almost all commercial metal–air batteries include zinc negative
electrode, and commercial iron–air primary battery is very difficult to be found.
The electrode reaction of iron in an alkaline electrolyte totally occurs at solid state
without involving the deposition–dissolution process, because of the low solubility of
the discharge products from iron, i.e., iron hydroxides and iron oxides. This property
of iron is a disadvantage for a primary battery, but a potential advantage for a
secondary battery because one need not worry about shape change phenomenon of a
negative electrode over cycles. Therefore, this battery system has rather been viewed
as an advanced secondary battery.
Iron–air secondary battery has been investigated as a candidate for the power source
of electric vehicles. Battery suppliers such as Matsushita, Swedish National
Development, and Westinghouse fabricated large-scale pilot cells during the 1980s.
The specific energy of the cell is as high as 75 Wh kg−1, which is too low to be
compared with the theoretical specific energy, even though the practical cell involves
positive electrode catalyst and electrolyte, which are not considered in a theoretical
system. Moreover, the rate capability and the cycle stability of such practical cells are
still not at a sufficient level. Iron negative electrode is mainly responsible for the low
specific energy and insufficient cycle stability, while air positive electrode is considered
to be responsible for the low rate capability. This type of battery system is still very
attractive as a post-lithium-ion battery because of its high theoretical specific energy.
In order to realize the practical cell system with expected properties, every factor,
from material preparation to cell fabrication, is required to be optimized. In this
article, the recent topics on the investigation about this battery system will be
introduced.

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SECONDARY BATTERIES – METAL-AIR SYSTEMS |


Bifunctional Oxygen Electrodes
L. Jöerissen, in Encyclopedia of Electrochemical Power Sources, 2009

Catalyst Systems
Bifunctional oxygen/air electrodes are used in electrically rechargeable metal–air
batteries. They are also relevant in the so-called regenerative fuel cells. Owing to their
high conductivity caused by the high mobility of protons in aqueous solution, alkaline
or acid electrolytes are preferred to neutral electrolytes.
Many synthesis routes have been investigated for the preparation of bifunctional
catalyst materials. The methods include precipitation from aqueous and nonaqueous
solvents, sol–gel processes, freeze drying, chemical spray pyrolysis, cathodic
sputtering, and electrochemical deposition. It is beyond the scope of this article to
discuss the synthesis methods in detail.

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Fuel Cells and Hydrogen Technology


F. Bidault, P.H. Middleton, in Comprehensive Renewable Energy, 2012

4.07.2.3 Non-Platinum Group Metal Catalysts


Recently, manganese oxides have attracted more attention as potential catalysts for
both fuel cells and metal–air batteries because of their attractive cost and good
catalytic activity toward O2 reduction. The investigation of different manganese oxides

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dispersed on high surface area carbon black showed low activity for MnO/C and high
activity for MnO2/C and Mn3O4/C. The higher activity of MnO2 was explained by the
occurrence of a mediation process involving the reduction of Mn(IV) to Mn(III),
followed by the electron transfer from Mn(III) to oxygen. The reaction is sensitive to
the manganese oxide/carbon ratio in which, at lower ratios, the reaction proceeds by
the two-electron pathway, evolving to an indirect four-electron pathway with
disproportionation of into O2 and OH− at higher catalyst/carbon ratios. The
catalytic activity for the disproportionation reaction has led to a new approach of dual
system catalysis in which one catalyst is used for the reduction of O2 through the two-
electron process producing , which is subsequently decomposed by MnO2,
leading to a four-electron process. The MnO2 catalytic activity was found to vary
following its crystalline structure in the sequence: β-MnO2 < λ-MnO2 < γ-MnO2 < α-
MnO2 ≈ δ-MnO2, in which higher activity seems to go with higher discharge ability
proceeding through chemical oxidation of the surface Mn3+ ions generated by the
discharge of MnO2 rather than through a direct two-electron reduction. γ-MnOOH
exhibits higher activity than γ-MnO2; this has been explained by the fact that
amorphous manganese oxide has more structural distortion and is more likely to
have active sites compared to crystalline manganese oxides.
Pyrolyzed macrocycles on carbon support have been studied in alkaline media
showing high activity toward the ORR. Cobalt phthalocyanine has been shown to
reduce oxygen with similar kinetics to that of Pt. Electrodes made of Cobalt/Iron
tetraphenylporphyrin (CoTPP/FeTPP) demonstrated good performance,
outperforming electrodes made of silver catalysts. Increased surface area and
structural changes are required to enhance the catalytic activity, which is obtained by
chemical and heat treatments of the carbon and the porphyrins. This high catalytic
activity was attributed to the combined effect of the macrocycle black and Co;
however, poor stability has been shown where the loss of Co appeared to be
important, leading to performance deterioration.
CoCO3 + tetramethoxyphenylporphyrin (TMPP) + carbon showed better performance
than CoTMPP + carbon confirming the fact that the structure of the metal macrocycle
is not responsible for catalytic activity, but its origin is due to the simultaneous
presence of the metal precursor, active carbon, and a source of nitrogen, supposed
already to be part of the catalytic process.
Perovskite-type oxides, which have an ABO3-type crystal structure, have shown a high
cathode activity in alkaline media proceeding by a two-electron pathway where
is further reduced. Good performance has been reported with different catalyst
composition such as La0.5Sr0.5CoO3, La0.99Sr0.01NiO3, La1 −XAxCoO3 (A = Ca, Sr),
Ca0.9La0.1MnO3 and Pr0.6Ca0.4 MnO3, and La0.6Ca0.4CoO3. The catalyst support
choice seemed to be crucial to obtain stable performance. Graphite supports
appeared less stable than high surface area carbon black.
A spinel is a ternary oxide containing three different elements named after the
mineral spinel MgAl2O4. The general structure is AB2O4 in which the choice of the B
cation is critical as it plays an important role in the activity of the catalyst. Studies of
MnCo2O4 catalysts have mainly indicated an ORR mechanism that involves a two-
electron process with formation. The catalytic activity depends greatly on the
preparation route; the decomposition of Co and Mn nitrates and subsequent heat
treatment is most commonly used.

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Manganese Oxides-Graphene Nanocomposites as


Advanced Supercapacitors
Wan Jeffrey Basirun, ... Sohail Ahmed, in Reference Module in Earth Systems and
Environmental Sciences, 2021

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Future perspective
Despite the promise shown by PC oxide materials such as MnO2 especially
composited with EDLC materials such as nanocarbons, it faces stiff competition from
battery manufacturers who prefer MnO2 as positive electrodes in alkaline batteries,
metal air batteries and hydrogen fuel cells. At present, none of the oxide materials are
commercially viable (Simon and Gogotsi, 2008) as SCs, compared to carbon materials
such as activated carbon due to the cheaper cost, ease of manufacturing and are
readily available from biomass. This is also coupled with the higher power density of
activated carbon materials which fulfills the functional role as SCs compared to MnO2
and RuO2 PCs with higher energy density. Moreover, SCs are not primary power
supply units but are merely secondary storage units which must be coupled with
primary sources such as batteries, fuel cells, wind energy, hydroelectricity and solar
cells, thus the utilization of MnO2 in SCs has less importance compared to the
primary power sources.
Nevertheless, a latest report “Supercapacitor Materials and Formats 2020–2040”
from IDTechEx shows that electric vehicle manufacturers predict SCs will have a large
market share especially with the bright prospects of electric vehicle manufacturing
and is estimated nearly 6 billion USD in 2040. The SC powered vehicle needs to only
recharge at the recharging station, and moreover SC are flexible enough to be fitted
in tight places which outstretch batteries (IDTechEx, 2020a). Another report
“Supercapacitor Markets, Technology Roadmap, Opportunities 2021–2041” from
IDTechEx reveals that SCs will eventually replace 10% of lithium ion batteries and
supersede the lead acid battery (IDTechEx, 2020b).
With the rising popularity of hydrogen fuel cell vehicles utilizing MnO2 as the positive
electrode for oxygen reduction electrocatalysts, a breakthrough in MnO2 SC
manufacturing in the industrial scale could be unlikely. However, with the recent
advancements of new oxygen reduction electrocatalysts such as metal organic
frameworks (MOF) (Yang et al., 2018) to replace MnO2 in metal air batteries and
hydrogen fuel cells, the commercial viability of MnO2 PC is not remote. The advent of
rechargeable or secondary zinc ion batteries incorporating perovskites, a material
used in solar cell technology, giving rise to rechargeable zinc-ion batteries using
sunlight, the replacement for the MnO2 positive electrodes in the non-rechargeable
or primary alkaline and metal air batteries could be realized, hence the dependency
toward MnO2 is further expected to decrease (Boruah et al., 2020).

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SECONDARY BATTERIES – METAL-AIR SYSTEMS |


Lithium–Air
S.J. Visco, ... L.C. De Jonghe, in Encyclopedia of Electrochemical Power Sources, 2009

The Lithium/O2 (Air) Battery


The lithium/air battery has a theoretical specific energy density of 5000–
11 000 Wh kg−1 depending on the nature of the electrolyte and reaction products
(Tables 1 and 2). Since lithium metal reacts rapidly with water, the geometric
construction of a lithium/air battery is quite different from that of other metal/air
batteries, including the commercial Zn/air cell. In the Zn/air battery, the anode
consists of zinc metal slurry containing concentrated aqueous potassium hydroxide
electrolyte. In the Zn/air battery, the basic electrolyte serves as an ionic medium and
minimizes corrosion of the zinc metal by water and oxygen, and the product of cell
reaction is also contained in the anode compartment whereas the cathode consists of
a GDE that facilitates the oxygen reduction reaction.

Table 1 . lithium/O2 and lithium/water battery couples

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Li/O2 in aqueous electrolytes

Basic electrolyte 4Li+O2+2H2O=4LiOH E=3.45 V

Acidic electrolyte 4Li+O2+4H+=2H2O+4Li+ E=4.28 V

Seawater (pH 8.2) 4Li+O2+2H2O=4LiOH E=3.79 V

Li/O2 in nonaqueous electrolytes

Li/water Li+O2=Li2O2 (peroxide) E=2.97 V

Basic electrolyte 2Li+2H2O=2LiOH+H2 E=2.22 V

Seawater (pH 8.2) 2Li+2H2O=2LiOH+H2 E=2.56 V

Table 2 . Theoretical specific energy for various metal/air couples

Comparative metrics Li Mg Al Ca Zn Fe

Ah g−1 3.86 2.21 2.98 1.34 0.82 0.96

Potential (V) 3.0 1.3 1.3 2.0 1.1 1.0

Wh kg−1 (anode) 11 600 2900 3900 2700 900 960

Wh kg−1 (anode+H2O) 5000 1600 1900 1800 900 730

Wh kg−1 (end of discharge) 3400 1200 1300 1400 730 600

In the lithium/air cell design, the PLE is immersed in electrolyte, which may be either
aqueous or nonaqueous in nature, and the product of cell discharge is contained in
the cathode compartment, which also has a GDE (see Figure 6). The aqueous
lithium/air design has a number of interesting advantages over Zn/air batteries,
including a higher open-circuit potential (Table 2), much higher specific energy, and
chemical isolation of the anode from the electrolyte, allowing the use of basic, neutral,
or acidic electrolytes. Most metal/air batteries suffer from corrosion of the anode by
water and oxygen once the battery is activated (exposed to ambient air); another
problem related to exposure to ambient is the process of carbonation where
atmospheric carbon dioxide reacts with potassium hydroxide to form potassium
carbonate (K2CO3), which precipitates in the GDE and may block oxygen transport.
Conversely, in the lithium/air system, the use of a PLE chemically isolates the lithium
metal anode, which prevents the self-discharge reaction with oxygen and allows the
use of neutral or acidic electrolyte that is not susceptible to carbonation (at least until
the cell is discharged into the basic regime). The discussion of lithium/air technology
can be divided into three parts: (1) aqueous lithium/air, (2) nonaqueous lithium/air,
and (3) submersible lithium/air. In order to be considered for real-world applications,
the lithium metal anode must be protected against moisture; hence only those
technologies that employ a PLE are discussed here.

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Figure 6. Schematic of lithium/air battery based on protected lithium electrode (PLE)


technology.

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Using Low-Cost UAVs for Environmental Monitoring,


Mapping, and Modelling: Examples From the Coastal
Zone
David R. Green, ... Billy J. Gregory, in Coastal Management, 2019

19.4 Batteries
Because most of the platforms and their attached systems are now mostly reliant
upon batteries, for example, LiPo (Lithium Polymer), developments in battery
technology have become essential to allow for longer flight duration and reliability.
There is currently considerable effort being put into developing battery technology
with rapid advancements; for instance, the ratio capacity to size is increasing, which
facilitates more power consuming activities such as longer flights and heavier
payloads (Gomez and Green, 2015). Various new battery technologies are also
emerging that are more compact and more lightweight alongside their extended life.
Metal-air battery technologies (e.g., zinc-air, aluminium-air, lithium-air) are being
developed. These batteries have valuable qualities that will benefit the UAV industry,
for example, high-density power. Graphene cells, although not yet commercially
available, also have potential for UAVs. For the moment, though, LiPo batteries of
varying sizes and capacities seem to dominate the market, although lithium sulfur
technology (Li-STM) is viewed as the next development
(www.barnardmicrosystems.com/UAV/engines/batteries.html). Within a very short
space of time, battery life, even for smaller UAVs (e.g., the DJI Phantom) has increased
the flight time from 5–8 min to 15–20 min, and even longer with some larger and
enhanced LiPo batteries. Naturally, larger UAVs with more payload and lift capacity
can extend this flight time further using multiple onboard battery packs. Other
sources of energy used by a few UAVs are fuel cells and solar power. Some even use
new technologies such as microgenerators, microturbines, and chemically powered
systems that may replace batteries in the future. Nevertheless, battery technology is
far from becoming obsolete and new designs introduced by battery manufacturers
now offer relatively light, high capacity and reliable sources of power (Gomez and
Green, 2015).

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PRIMARY BATTERIES – AQUEOUS SYSTEMS | Zinc–


Air
H. Arai, M. Hayashi, in Encyclopedia of Electrochemical Power Sources, 2009

Principle
The simplest expression of zinc–air battery reactions is as follows:

[1]

[2]

[3]

where SHE refers to standard hydrogen electrode. The theoretical specific capacity of
eqn [3] reaches 0.66 Ah g−1 (1 Ah g−1=3.6×103As g−1), giving a theoretical specific
energy of 1.1 Wh g−1. This is one of the highest values for any battery reaction. An
aqueous alkaline solution is used for the electrolyte, because a hydroxide ion (OH−)
transfer occurs in eqns [1] and [2]. There is no net water consumption/production in
eqn [3], unlike the discharge reaction of zinc–carbon cells shown in eqn [4]. The result
is that there is essentially no change in electrolyte concentration in zinc–air batteries
during discharge:

[4]

Among the candidates for metal/air battery anodes, zinc is adequately a base metal
and can be used in aqueous electrolyte solutions. In fact, as predicted by the negative
potential corresponding to eqn [2], zinc is thermodynamically unstable in aqueous
media and zinc corrosion (self-discharge) can occur as shown below:

[5]

Nevertheless, the zinc corrosion rate is slow in alkaline media


and the system is substantially stable, because the overvoltage
required for hydrogen evolution on a metallic zinc surface is
sufficiently high. Lead, a much less basic metal than zinc, also
has a high overvoltage for hydrogen evolution on its surface;
however, it corrodes in lead–acid batteries owing to the highly
acidic electrolyte solutions used in the batteries.
The specific capacity of zinc is not very large (0.82 Ah g−1) when compared with other
candidates for metal/air battery anodes, such as lithium (3.86 Ah g−1) and aluminum
(2.98 Ah g−1), but these lighter elements are mostly unstable in aqueous solutions.
The existence of zincate species with Zn2+, such as ZnO, Zn(OH)2, ZnO22−, and
Zn(OH)42−, depends on the thermodynamic conditions (OH− concentration and
temperature) and is also affected by kinetics, as the supersaturation of zincate is
generally known. Regardless of the zincate formula, the anodic reaction of zinc has
little influence on the reaction potential, as shown in the following example:

[6]

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Oxygen is an ideal cathode active material. It has strong oxidizing power, is light in
weight relative to its large specific capacity (3.35 Ah g−1), and poses essentially no
problems in terms of resources or environment. However, the direct electrochemical
(four-electron) reduction to hydroxide ions described in eqn [1] is generally slow and
occurs only in the presence of special catalysts. In the absence of such a catalyst (e.g.,
on the surface of a carbon substrate), the electrochemical (two-electron) reduction to
peroxide ions is dominant as the cathodic reaction of the zinc–air battery:

[7]

Thus formed peroxide ions are generally unstable and are decomposed via the
disproportionation reaction of oxygen to produce hydroxide ions and molecular
oxygen:

[8]

The decomposition of the peroxide ions in eqn [7] is also catalyzed by the typical air
electrode catalyst. The low actual discharge voltage of zinc–air batteries (1.3 V) can be
partly ascribed to this electrochemical (two-electron) reduction to peroxide ions.

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Polymers for Advanced Functional Materials


J. Yan, ... L. Zhi, in Polymer Science: A Comprehensive Reference, 2012

8.17.3.3.3 Catalysis
Nanometer -scale dimensions of metal particles are favorable for the enhanced
diffusion rates and fast electron transfer kinetics;, which are critical in the fields of
catalysis research. Therefore, CNTs are highly attractive material as both catalyst
supports and catalytic active materials.
Girishkumar and co-workers285 have prepared Pt nanoparticles through
electrodeposition on optically transparent electrodes of SWNTs for both methanol
oxidation and oxygen reduction reaction. These electrodes displayed greatly improved
catalytic performances, and the methanol oxidation currents were about 10 times
higher when the same amount of Pt nanoparticles was supported on SWNTs.
Moreover, the current values detected for oxygen reduction reactions were higher by
a factor of 1.5 for Pt nanoparticles supported on SWNT compared to unsupported Pt
particles.263
Gong’s group286 at Chinese Academy of Sciences has successfully functionalized CNTs
with MnO2 and synthesized an electrochemically functional and structurally uniform
nanocomposite. The resultant nanocomposite has been found to possess an excellent
electrocatalytic activity toward 4e reduction of O2 in alkaline solution and could be
highly applicable as an air electrode material for the electrocatalytic reduction of O2 in
alkaline fuel cells and metal/air batteries.287
In 2005, Cui and co-workers288 studied the electrocatalytic oxygen reduction reaction
by electrodepositing Pt nanoparticles on MWNTs. A significant positive shift in oxygen
reduction potential and a concurrent increase in oxygen reduction current have been
observed. Pt nanoparticles deposited on MWNTs also exhibited enhanced transfer
rates of electrons as well as stability for methanol oxidation.263,289
Use of bimetallic catalysts such as Pt–Ru has been commonly accepted in order to
improve catalytic efficiency and protect Pt from CO poisoning. Homogeneously
dispersed catalyst nanoparticles with a size range from 60 to 80 nm were prepared by
potentiostatic methods in 0.5 M H2SO4 aqueous solutions of ruthenium chloride and

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chloroplatinic acid at a potential of –0.25 V.290 The Pt–Ru particles were found to
exhibit higher catalytic activity and stability compared to pure Pt nanoparticles.
Consequently, it is reasonable to enhance the catalytic activity by incorporating
bimetallic nanoparticles into CNTs.263
Functionalized CNTs are also widely investigated in the petrochemical and fine
chemical industries for the synthesis of an extensive kind of chemicals. In 2005,
Zhang’s group292 found that CNTs modified with Co nanoparticles were highly
catalytically active and regioselective for the formylation of 1-octene. Tessonnier and
co-workers114,291 reported the intriguing catalytic performances of Pd nanoparticles
deposited completely on the inner walls of MWNTs for the selective hydrogenation of
cinnamaldehyde to hydrocinnamaldehyde (Figure 31). These authors also found that
the Pd–MWNTs showed a notable increase in selectivity, with hydrocinnamaldehyde
being the major (> 80%) product. In 2004, Ye et al.293 observed that the Pd–MWNTs
were excellent catalysts for the hydrogenation of olefins, including the conversion of
stilbene into 1,2-diphenylethane, with a conversion efficiency of ∼96% after 10 min
exposure.

Figure 31. Various reaction pathways in the hydrogenation of cinnamaldehyde,


possible products, and the ratio of these products formed when using Pd
nanoparticles supported on MWNTs.

Adapted with permission from Tessonnier, J. P.; Pesant, L.; Ehret, G.; et al. Appl.
Catal. A Gen. 2005, 288, 203.291 Copyright 2005, with permission from Elsevier.

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