https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev.

, 2018, 62, (2), 134–149

www.technology.matthey.com

Rechargeable Multi-Valent Metal-Air Batteries

A review of research and current challenges in secondary multivalent
metal-oxygen batteries

By Laurence J. Hardwick* hereafter referred to as metal-O2 batteries, could

Stephenson Institute for Renewable Energy, play an increasingly important role as an energy
Department of Chemistry, The University of storage technology in consumer electronics,
Liverpool, Peach Street, Liverpool, L69 7ZD, UK electric vehicles, stationary storage and defence,
because of their high specific energy (energy
Carlos Ponce de León# per unit weight) and energy density (energy per
Faculty of Engineering and the Environment, unit volume). A schematic representation of the
University of Southampton, Highfield, rechargeable metal-O2 cell is shown in Figure 1.
Southampton, SO17 1BJ, UK In general, for non-aqueous metal-O2, on
discharge, metal ions formed at the metallic anode
Email: *[email protected]; are transported across the electrolyte and into the
#
[email protected] pores of the air cathode. O2 from the atmosphere
enters the cathode, and dissolves into the
electrolyte within the pores. It is then reduced at
Rechargeable metal-oxygen cells could exceed the porous carbon electrode surface by electrons
the stored energy of today’s most advanced from the external circuit and combines with the
lithium-ion cells. However challenges exist that metal ion (Mn+) from the electrolyte, leading to
must be overcome to bring this technology the formation of a solid metal oxide (MxOy) as the
into practical application. These challenges final discharge product. Remarkably the reaction
include, among others, the recharge and is, to varying degrees, reversible. The metal
cyclability efficiency, materials development and oxide can be electrochemically oxidised, releasing
improvements in fundamental understanding oxygen gas, thus making this an energy storage
of the electrochemistry and chemistry inside device.
the cell. The common challenges for the anode, In aqueous metal-O2, because the solubility of
including corrosion, passivation and dendrite oxygen in water is low at atmospheric pressure
formation and those for the air cathode and the (0.2 mM, at 25°C, 1 atm.) it is necessary to use
electrolyte are summarised in this review for oxygen in the gas phase not the liquid. Oxygen
cells based on magnesium, calcium, aluminium, from the atmosphere diffuses into the porous
silicon, zinc and iron. carbon electrode, known as the gas diffusion
electrode, by difference in pressure of oxygen
between the outside and inside of the cell.
1. Introduction
Catalysts facilitate the reduction of oxygen to
Unlike a conventional battery where the reagents hydroxyl ions (in an alkaline electrolyte), with
are contained within the cell, metal-air batteries electrons generated from the oxidation of the
utilise dioxygen (O2) from the atmosphere, and metal anode. This may lead to the precipitation of
consequently can be thought of as a battery-fuel a solid metal hydroxide (Mx(OH)y) within the cell.
cell hybrid. Rechargeable metal-air batteries, The process is known as a three-phase reaction:

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https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

(a) (b)

Electrocatalyst
supported on C black
–
e e–
e– e–
Electrocatalyst
Hydrophobic layer
Air cathode and current collector

Metal Metal
anode anode
M+ O2 OH– O2

Electrolyte Aqueous
electrolyte

M1 Mn+ + ne– M + yOH–1 M(OH)y + ye–

MxOy
xMn+ + ne– + y/2O2 1 MxOy Gas diffusion electrode, ca. 0.5 mm

1
/2O2 + 2e– + H2O 1 2OH–

Fig. 1. Typical metal-O2 batteries: (a) non-aqueous; and (b) aqueous

catalyst (solid), electrolyte (liquid) and oxygen as it will either be precipitated out by hydroxide
(gas). A comparison of the phase boundaries of ions, or form a negatively charged complex, in
aqueous and non-aqueous metal-O2 batteries is the vicinity of the anode (for example the zincate
shown in Figure 2. anion: Zn(OH)42–), which will never reach the
The reactions in non-aqueous and aqueous cathode.
metal-O2 cells are very different, and as Despite the recent major research activity
such present differing challenges to enable into rechargeable Li-O2 cells in particular (1–3),
their technological realisation, which will be metal-O2 batteries have in fact been under
discussed further within this review. Notably in consideration from as early as 1868, with the first
non-aqueous electrolytes the oxygen reduction demonstration of a Zn-O2 battery by Leclanché
at the cathode results in the formation of a metal (4). Since this time some metal-O2 technologies
oxide precipitate within the porous cathode itself. have moved from a purely academic interest to
However, in alkaline aqueous electrolyte the a commercial product, most notably the primary
multivalent metal ion does not reach the cathode, Zn-air battery.

(a) (b)
Organic
electrolyte
Aqueous
Air O2 electrolyte M+ O2
O2 M+
O2 ion
MxOy

e– e–

Solid Solid

Fig. 2. Phase boundaries for (a) aqueous; and (b) non-aqueous metal-O2 batteries

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A substantial amount of work has been carried Table I, where they are compared with those
out on metal-O2 batteries, but among the present for present day Li-ion cells. In the case of the
challenges is the fundamental understanding and non-aqueous Li-O2 cell, a value of 11,586 Wh kg–1
subsequent control of the electrochemistry and is often quoted; however this is based on the mass
chemistry that takes place within metal-O2 cells of Li metal alone. All metal-O2 cells gain mass (O2)
and the discovery of new materials that deliver as they discharge, so the mass of O2 should be
the desired superior lifetime and performance (at included for all metal-O2 systems.
a competitive cost). There are already a number The claim is often made that the increase in specific
of highly detailed reviews and articles on Li-O2 energy, in particular over conventional battery
(1, 5–8) and Na-O2 (9, 10), as well as primary systems (Li-ion), is that the reactant dioxygen does
Zn-air systems (11). This review focuses on the not have to be carried within the cell. However, this
recent work in rechargeable multivalent (+2, is a misconception. The leap forward in theoretical
+3, +4) metal-O2 cells, their operation, energy specific energy on migrating from Li-ion to either
storage capability and the challenges they face in aqueous or non-aqueous metal-O2 (using Li-O2 as
realisation of becoming a practical technology. the example) arises because Li2O2 in the cathode
stores more Li, and hence charge, than say LiCoO2
per unit mass and Li metal stores more charge per
2. Theoretical Energy Storage
unit mass than a graphite (C6Li) anode. Theoretical
The theoretical specific energies (Wh kg–1) energy densities for aqueous metal-O2 cells are
(gravimetric energy densities) and energy also attractive. The theoretical energy density
densities (Wh dm–3) (volumetric energy densities) can be calculated by taking into account both the
for a range of metal-O2 batteries are given in volume of the metallic anode in the charged state

Table I D
 ata for Conventional Batteries Electrochemical Reactions for Common Metal-O2
Couples that Form the Basis of Energy Storage Devices

Cell Theoretical Theoretical energy

Battery voltages, specific energy, density, Wh dm–3 (active
V Wh kg–1 components in brackets)

Li-ion Today
½C6Li + Li0.5CoO2 = 3C + LiCoO2 3.8 387 1015

Li metal/LiCoO2
½Li + Li0.5CoO2 = LiCoO2 3.9 534 2755

Li-O2 (aq) 2234

3.2 3582
2Li + ½O2 + H2O = 2LiOH (Li + H2O + LiOH)

Li-O2 (non-aq)
2Li + O2 = Li2O2 2.959 3457 3459 (Li + Li2O2)
4Li+ O2 = 2Li2O 2.913 5226 3823 (Li + Li2O)

Mg-O2 (aq) 3.11 2859 1671 (Mg + H2O + Mg(OH)2)

Mg+ ½O2 + H2O = Mg(OH)2 1.2a 1103 645 (Mg + H2O + Mg(OH)2)

Ca-O2 (non-aq)
Ca + O2 = CaO2 3.38 2514 2403 (Ca + CaO2)

Al-O2 (aq) 2.71 2794 1160 (Al + H2O + Al(OH)3)

2Al + ³/²O2 + 3H2O = 2Al(OH)3 1.2a 1237 514 (Al + H2O + Al(OH)3)

Si-O2 (ionic liquid) 2.39 4264 2492 (Si + SiO2)

Si + O2 = SiO2 1.1a 1962 1146 (Si + SiO2)

Fe-O2 (aq)
1.28 764 715 (Fe + H2O + Fe(OH)2)
Fe + ½O2 + H2O = Fe(OH)2

Zn-O2 (aq) 6091 (ZnO)

1.65 1086
Zn + ½O2 = ZnO 2316 (Zn + ZnO)
a
Experimentally recorded potentials on discharge of specific metal-O2 cells – the theoretical energy storage of these systems are
subsequently diminished (in italic). Theoretical energy density includes volume of all active components within the cell. Data taken from
(1) or calculated directly from open source thermodynamic data.

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and the volume of the discharge product (Mx Oy results from the oxidation of the metal in an
or Mx(OH)y) formed from 100% utilisation of the aqueous environment, either to a soluble metal
anode. When H2O is involved in the reaction, its ion or complex or to an insoluble oxide, hydroxide
volume requirement should also be considered, or other salt. In metal-O2 batteries, the oxidising
which lowers maximum energy densities of aqueous agent is commonly dioxygen, proton or water;
systems close to present day Li-ion. hence the overall chemical change can occur via
The theoretical energy density is also greater for one or more of the reactions in Equations (i)–(iv):
Li-O2 than Li-ion but the gain is not as great as
M + n/4O2 + n/2H2O → Mn+ + nOH–(i)
for specific energy. Certainly if the lithium metal
anode would operate successfully in a Li-O2 cell,
M + n/4O2 + nH+ → Mn+ + n/2H2O(ii)
then the positive energy storage benefit for the Li
metal/LiCoO2 cell would also be realised (Table I),
M + nH+ → Mn+ + n/2H2(iii)
as the energy density will be comparable to most
metal-O2 cells.
M + nH2O → Mn+ + n/2H2 + nOH–(iv)

Oxidation by a proton can be avoided by the use

3. Common Challenges of
of alkaline aqueous electrolytes (Equation (iv)).
Rechargeable Metal-Air Cells
An example of corrosion is given for the Fe-O2
3.1 Challenges for the Metallic Anode cell in Equations (v)–(ix). During spontaneous
dissolution of iron, the electrode gradually
Metallic anodes have been studied for many becomes coated with a Fe(OH)2 film as a result of
decades for numerous alternative battery systems the following corrosion reaction:
other than metal-O2, and the main challenges are
Fe → Fe2+ + 2e–
well understood. The common issues with metallic
Ec = –0.44 V vs. SHE (v)
anodes are corrosion, passivation and dendrite
formation (Figure 3).
2H2O + 2e– → 2OH– + H2
Ea = –0.83 V vs. SHE (vi)
3.1.1 Corrosion
Overall:
Corrosion of the metal anode is the major side
reaction that limits the performance and shelf Fe + 2H2O → Fe(OH)2 + H2
life of metal-O2 cells. Most commonly corrosion Ecell= +0.39 V vs. SHE (vii)

Dense MxOy
Electrolyte Electrolyte
surface layer

O2 + 4e– + 2H2O " 4OH– Ions M " Mn++ ne– Mn+

Cathodic e– Anodic
zone zone
Metal, M Metal, M

Corrosion Passivation

Risk of short circuit

Uneven replating of metal Growth of dendritic structures
Mn+ + ne– " M

Metal, M Metal, M Metal, M

Dendrite formation

Fig. 3. Schematic showing corrosion, passivation and dendrite formation processes at metal anode

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Remembering that for a corrosion reaction to be enough conductivity to deliver electrons to the
spontaneous: reaction site efficiently with low overall impedance.
High surface areas imply small pores that could
Ecell = Ec – Ea > 0 (viii)
become blocked by solid metal oxides, such as
CaO2, so a compromise is necessary between high
With DG = –nFEcell = –75.5 kJ mol–1 (ix)
active surface area and adequate pore size. For
Therefore as DG < 0, the reaction is practical metal-O2 cells, an exterior O2 permeable
thermodynamically favourable. membrane may be required to prevent the ingress
of water and carbon dioxide, whilst still allowing
the free passage of oxygen. In general the porous
3.1.2 Passivation
structure of the air cathode is not optimised for
Soluble species formed at the air cathode can gas evolution. The mechanical pressures, which
migrate across to the anode where they can be the carbon structure is subjected to as a result
reduced either chemically or electrochemically to of the evolution of dioxygen produced trying to
form a non-conductive layer on the metal surface escape the electrode, will cause mechanical
increasing the internal electrical resistance of the breakdown of the electrode, in addition to the
cell and preventing metal dissolution. high positive potential of oxygen evolution that
leads to carbon corrosion.
In aqueous metal-O2 air cathodes, a homogenous
3.1.3 Dendritic Formation and
distribution of a nano-sized catalyst is required to
Deformation
maximise the performance by increasing the round-
During the cycling of the metallic anode, the trip efficiency by lowering the voltage gap between
metal ion will not necessarily be plated where it charge and discharge processes (12). The structure
has been stripped. As a consequence the metal of the air cathode is critical in order to maximise
electrode will start to change shape; its surface will power capability. Nonetheless, the risk of mechanical
roughen, producing an electrode with an uneven degradation of the air cathode via O2 evolution will
thickness. The restructuring of the metal will lead increase at higher current densities. In aqueous
to the production of zones in the metal anode, systems gas diffusion electrodes are employed in
which become less active, resulting in loss of which the gas is carried in hydrophobic channels
performance. After repeated stripping and plating then dissolves in the electrolyte within hydrophilic
cycles, shedding of active material occurs leading channels that are in very close proximity. In this
to an irreversible loss of capacity. In worse cases way the O2 is transported mainly in the gas phase,
the roughened surface results in dendritic growth rather than the much slower diffusion in the liquid.
of the metal which can eventually penetrate the Assuming a suitable gas diffusion electrode that
cells’ glass fibre separator and then form a short ensures facile O2 transport can be constructed, then a
circuit with the air cathode. In aqueous systems high electrode surface area is necessary. The proper
this will result in the end of life of the cell and optimisation of the air cathode should lessen the
it will need to be replaced. In non-aqueous cells risk of electrode flooding from the electrolyte which
the result can be more catastrophic with the would lead to a reduction in oxygen accessibility.
short-circuit leading to thermal runaway. A further challenge is to prevent the ingress of
CO2 which will lead to carbonate formation within
the air cathode through reaction with the alkaline
3.2 Challenges for the Air Cathode
electrolyte.
The challenges for the air cathodes for both
non-aqueous and aqueous metal-O2 cells are
3.3 Electrolytes for Metal-O2 Batteries
shown in Figure 4. For non-aqueous systems a
typical air cathode is comprised of a high surface Understanding, controlling and hence eliminating
area carbon mixed with a polymeric binder. The side reactions in metal-O2 cells is a significant
porous carbon air cathode is required to ensure undertaking. The electrolyte must be stable to O2
a large electrolyte/electrode surface area and and its reduced species, as well as compounds that
accommodate the insoluble discharge product form on discharge; it must exhibit sufficient M+
(M x Oy), as well as to facilitate oxygen diffusion conductivity, O2 solubility and diffusion to ensure
to the reaction site through the cathode film. In satisfactory rate capability, as well as being able to
addition, the porous carbon network must provide wet the electrode.

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(a) Substrate effects Pore design Electrolyte

•• Forming the pure desired •• Heirarchical pore structure •• Wide electrochemical
discharge product •• Efficient diffusion of O2 into stability window
•• Minimisation of side pores •• Solvent and/or salt stable
reactions •• Avoid pore blockages against intermediate species
•• Surface vs. solution
mechanism
Reaction pathway •• Conductivity
Voltage gap between •• Volatility, evaporation from
discharge and charge cell
processes H2O, CO2 •• O2 solubility, diffusivity

Charge
O2
Potential

O2 permeable external membranes

•• Allow the passage of O2 but prevents
Discharge the ingress of major contaminants
•• Stable against electrolyte
Capacity •• Stable against reduced oxygen species
•• Prevent evaporation of electrolyte

(b)
Electrolyte Catalysts
•• Drying out through •• Sluggish oxygen reactions
water evaporation to •• Limitations of energy/power
open air H2O and efficiency
•• Air electrode •• Optimisation of type,
flooding through distribution, loading
electrolyte ingress
into air cathode OH– O2
pores leading to Side reactions from air
decrease in oxygen •• Atmospheric CO2 reacts
accessibility with alkaline electrolyte
•• Optimisation of gas CO2
leading to carbonate
diffusion layer and precipitates
hydrophobic layer

Fig. 4. Challenges facing: (a) the non-aqueous; and (b) the aqueous air cathode

The characteristics which a suitable metal-O2 cell Developing stable electrolytes that fulfil most, if
electrolyte must fulfil are listed below: not all, of the above criteria remains one of the
• resistive to nucleophilic attack from superoxide major research challenges in this field.
intermediates
• able to dissolve the electrolyte salt to sufficient
4. Alkaline-Earth Metal-O2
concentration. In other words it should have a
high dielectric constant (e) 4.1 Magnesium-O2
• high ionic conductivity (>1 mS cm–1) in order
to minimise internal resistance Present Mg-O2 research is limited and recent
• for liquid electrolytes, it should have low studies have focused on non-aqueous systems,
viscosity h, to facilitate mass transport magnesium alloys, suitable stable electrolytes and
• high O2 solubility and diffusivity bifunctional electrocatalysts for oxygen reduction
• stable in a wide electrochemical potential (13–18). A recent review article summarises the
window research to date (19).
• good thermal and chemical stability For the aqueous based system the predicted cell
• compatibility with other cell components voltage, according to Equations (x)–(xii), is 3.11 V,
• low cost, low toxicity and low flammability. corresponding to a specific energy of 2859 Wh kg–1:

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Anode: coworkers (21). Recently Ponrouch et al. (22)

demonstrated reversible Ca plating in an organic
Mg → Mg2+ + 2e–
carbonate solvent with Ca(BF4)2 salt at 100°C
Ea = – 2.7 V vs. SHE (x)
and this has reignited research in calcium-based
Cathode: battery systems. In particular, electrochemical
studies on the cathode side have followed (23, 24)
O2 +4e– +2H2O → 4OH–
that show some reversibility. However, finding an
Ec = 0.401 V vs. SHE (xi)
electrolyte that is good from reversible Ca plating/
Total: stripping and oxygen reduction/evolution reactions
remains a major task. The challenges facing
2Mg + O2 + 2H2O → 2Mg(OH)2
non-aqueous alkaline-earth metal-O2 cells in
Ecell = 3.11 (xii)
particular are summarised in Figure 5.
As a primary battery, in aqueous solutions, In aqueous-based systems, calcium metal
Mg-O2 suffers from high polarisation resulting corrodes rapidly in water and Ca-O2 batteries
in a practical cell voltage of 1.2 V. Despite the use an electrolyte containing 2:1 methanol:water
advantages of magnesium being abundant and a ratio to decrease its reactivity. This electrolyte
very active lightweight metal with relatively low with 10% (NH4)2SO 4 plus 5% LiCl was used with
toxicity, the cell has low coulombic efficiency due to a platinum air breathing electrode to produce a
the slow kinetics of the oxygen reduction and the cell able to deliver 70 mA cm–2 at 1 V. Due to the
high rates of magnesium corrosion. Magnesium can limitations of the air cathode, a high temperature
be mechanically replaced, but whilst operational Ca-O2 using a Ca-Si anode alloy in a molten salt
suffers from irreversible polarisation and high with 29% mol of CaO-71 mol CaCl2 stabilised with
self-discharge rates. In alkaline electrolytes, 5 wt% Zr-O at 850°C has been proposed (25).
magnesium anodes passivate, but still show high The charge-discharge processes are associated
corrosion rates, therefore aqueous Mg-O2 systems to the reversible formation of CaSi and CaSi2,
use a sodium chloride solution. Even in this Equation (xiii):
electrolyte, pure magnesium passivates over time
2CaSi + 1/2O2 CaO + CaSi2(xiii)
and therefore some alloys such as Mg/Al/Zn have
been proposed to mitigate against this (20). With an open circuit voltage of 2.28 V the battery
operated for 52 h with a Faradaic efficiency of 95%.
Other room temperature Ca-O2 batteries use Ca or
4.2 Calcium-O2
Ca alloy in acetonitrile or DMF and gas diffusion
Until fairly recently there were no reports of cathode (Co, Ni, Fe, and/or Mn or transition metal
reversible Ca metal stripping/plating in an organic porphyrin or phthalocyanines). Cooper et al.
solvent. The oxide passivation layer on Ca metal (26) reported the passivation of Ca electrodes in
was found to be electronically and ionically 3 mol dm–3 NaOH but the addition of Cl– produced
insulating within a seminal study by Aurbach and stable electrodes. The open circuit voltage of the

Discharge
Anode
e– Cathode
Mg and Ca
•• Discharge
•• Formation of e– – + products not fully
passivating oxide characterised
layer
•• Use of alloys
M “M2+” O2 Cell
•• Optimal system not
Electrolyte yet established
•• Search for stable Non-aqueous Porous Mx(Oy)z
electrolytes electrolyte carbon

Fig. 5. Challenges for non-aqueous alkaline-earth metal-air batteries

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cell was 3.1 V for <3 mol dm–3 OH–, <0.1 mol of the anode. The competing electrochemical
dm–3 Cl– and coulombic efficiency proportional to processes on the Al surface are:
the concentration of Na approaching 100%. Based • formation and/or dissolution of an initial Al2O3
on these results the Ca-O2 cell might operate at a and subsequent Al(OH)3 layer
thermodynamic efficiency of 35–40% for a cathode • oxidation of Al to Al3+
polarisation of 0.4 V and 100 mA cm–2 current • formation of corrosion species – Al(OH)4– and
density. Al(OH)3
• parasitic corrosion resulting in H2 formation via
water reduction.
5. Aluminium-O2
Self-corrosion at open circuit prevents the
The ideal reactions for the Al-O2 battery during storage of wet Al-O2 cells and reduces their
discharge are Equations (xiv)–(xvi): discharge efficiency. The corrosion and oxidation
Anode: of Al in alkaline electrolytes depends on electrolyte
properties, temperature and purity. Indeed one of
Al + 4OH– → Al(OH)4– + 3e–
the methods for suppressing parasitic corrosion
Ea = –2.31 V vs. SHE (xiv)
whilst maintaining the electrode activity can be
Cathode: achieved by employing high purity aluminium
(>99.999% purity) or by alloying the aluminium
O2 + 2H2O + 4e– → 4OH–
with minor amounts of indium, gallium, zinc,
Ec = 0.401 V vs. SHE (xv)
magnesium, tin or thallium. This of course will
Total: dramatically increase the cost of the anode (29).
It is essential to the battery performance that
4Al + 3O2 + 6H2O → 4Al(OH)3
both the Al anode and air cathode can operate at
Ecell = 2.71 V (xvi)
a current density greater than 100 mA cm−2. With
The theoretical specific energy is 2793 Wh kg–1 a neutral brine electrolyte, the Al(III) is largely
considering the product Al(OH)3 and the cell voltage formed as a solid oxide and/or hydroxide and the
is 2.71 V. But in practice the available specific energy performance of the battery depends critically on
is lower as the operating voltage is usually around the form of this precipitate; it must not form a
1.1 V. The battery is a primary energy storage passivating film on the aluminium surface nor inhibit
device since the electrodeposition of aluminium the air cathode. In addition, the Al material used as
from alkaline solutions is not thermodynamically the negative electrode must be stable to corrosion
feasible due to its negative standard potential, during battery storage, i.e. the following chemical
leading to hydrogen evolution before any aluminium reactions (Equations (xix)–(xx)) should not occur
can be deposited. Mechanically recharging has been at open circuit potential or during discharge:
proposed by replacing the anode. Alternatively
4Al + 3O2 + 6H2O → 4Al3+ + 12OH–(xix)
hydrogen evolution could be potentially removed
by using ionic liquid electrolytes, where some
2Al + 6H2O → 2Al3+ + 3H2 + 6OH–(xx)
studies show good plating reversibility (27).
The performance of an Al-O2 battery is The competing demands of stability to corrosion
determined by the electrochemical and corrosion and rapid anodic dissolution makes difficult the
properties of the aluminium alloy electrode and identification of the appropriate aluminium alloy.
the associated hydrogen gas evolution (28), Several alloys to suppress the hydrogen evolution
Equations (xvii)–(xviii): and lower the self-corrosion of aluminium have
been identified. Nevertheless the high cost of
2H2O + 2e– → 2OH– + H2
these high-purity aluminium alloys still restricts
E = –0.83 V vs. SHE (xvii)
the commercialisation of Al-O2 batteries and its
2Al + 6H2O → 2Al(OH)3 + 3H2(xviii) use has been limited. Figure 6 shows typical
challenges and performance of an Al-O2 battery,
Aluminium passivates in air or in aqueous solutions using gel electrolyte, bipolar electrodes and a
by formation of an oxide layer of several nanometre flowing electrolyte (30).
thicknesses which is detrimental to battery Despite the operational barriers of the aluminium-
performance and restricts the ability to achieve air battery mentioned above, a number of studies
the reversible potential causing delayed activation dealing with hydrogen evolution and rechargeable

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Discharge
Anode e–
Cathode
Problems of aluminium
e– – + •• Al(OH)3 precipitate
•• Formation of nm thick blocking pores
oxide layer (Al2O3) 3OH– OH– 4OH–
•• Parasitic corrosion of Al
resulting in H2 evolution O2
Al Rechargeability
•• Al(OH)3 precipitate on
surface Al(OH)3 Al(OH)4– 2H2O •• Mechanical regeneration
of Al
Alkaline or Porous
neutral carbon +
electrolyte catalyst
Electrolyte Cell
2.0
•• Challenge to reversibly Gel electrolyte •• Open circuit potential
1.8 Bipolar cell
plate Al in most known Flowing reduced from 2.71 V to ca.

Cell voltage, Ecell, V

electrolytes, therefore electrolyte 1.6 V due to competing
1.6
only primary cell electrochemical reactions
1.4 •• Practical operating voltages
of ca. 1.1 V
1.2 •• Self-corrosion at open
1.0 circuit prevents the storage
of wet Al-air cells
0.8

0.6
1 10 100
Current density, j, mA cm–2

Fig. 6. Challenges for Al-air and typical performance curves for different primary Al-air configurations.
Performance curve data provided by C. Ponce de Leon taken from (30) © Elsevier 2013

issues have been reported. Mori (31–33) for system has a specific energy of 4264 Wh kg–1. It
example, used ceramic barriers such as aluminium consisted of a doped silicon anode and carbon-
oxide or aluminium tungsten oxide between the based air cathode with the addition of MnO2 as
aqueous electrolyte, the aluminium anode and the an oxygen reduction reaction (ORR) catalyst. The
air cathode in order to suppress the accumulation of electrolyte employed within the cell was a room
byproducts. However, the current densities remained temperature hydrophilic ionic liquid, 1-ethyl-3-
low. The same author also suggested aluminium methylimidazolium oligofluorohydrogenate (EMI
terephthalate metal-organic framework (MOF) for (HF2.3F)), which is synthesised from EMI Cl and HF.
the air cathode and 1-ethyl-3-methylimidazolium The discharge of the cell results in the oxidation
chloride as an ionic liquid electrolyte in order to of silicon at the silicon wafer anode and in the
obtain more stability over repeated electrochemical reduction of atmospheric oxygen at the air cathode.
reactions. Deyab used 1-allyl-3-methylimidazolium The room temperature ionic liquid (RTIL) electrolyte
bis(trifluoromethylsulfonyl)imide ionic liquid to anions participate in both electrode reactions and
overcome the hydrogen evolution reaction (HER) are therefore key in permitting the operation of the
(34). They suggested that 1.5 × 10–3 mol dm–3 battery.
added to a 4.0 mol dm–3 NaOH electrolyte resulted
The reaction at the anode is Equation (xxi):
in an enhanced capacity from 1720 to 2554 mA
h g–1. Other attempts to use aluminium include a Si + 12(HF)2F– → 8(HF)3F– + SiF4 + 4e–(xxi)
mechanical rechargeable Al-O2 cell consisting of
And the reactions at the cathode are Equations
wedge anodes able to reach up to 1500 W h kg–1
(xxii)–(xxiii):
energy density (35).
O2 + 12(HF)3F– + 4e– → 2H2O + 16(HF)2F– (xxii)
6. Silicon-O2
SiF4 + 2H2O + 4(HF)2F– → SiO2 + 4(HF)3F– (xxiii)
A Si-O2 battery was first reported by Ein-Eli and
co-workers in 2009 (36) and theoretically the Leading to the overall reaction, Equation (xxiv):

142 © 2018 Johnson Matthey

https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

Si + O2 → SiO2 (xxiv) capacity of 1206 mAh g–1 at 0.1 mA cm–2 with an

operating voltage of 1 V being reported, Equations
Cells tested show an open circuit potential of (xxv)–(xxvii).
ca. 1.4 V rather than the theoretically predicted Anode:
2.89 V, the operating potential for this cell is in the
Si + 4 OH– → Si(OH)4 + 4e–
0.8–1.1 V region. The role of water in the Si-O2 cell
Ea = –1.69 V vs. SHE (xxv)
is central in the production of SiO2 at the cathode,
see Equation (xxiii). SiO2 formation results in the Cathode:
reaction of H2O with a fluororacidic anion [(HF)2F–]
O2 + 2H2O + 4e– → 4OH–
and with SiF4. Indeed it has been demonstrated
Ec = 0.401 V vs. SHE (xxvi)
that this ionic liquid electrolyte with an addition
of 15 vol% of water can increase cell capacity to Leading to the overall reaction:
72.5 mAh cm–2 from 50 mAh cm–2 for water free
electrolyte, at a current density of 0.3 mA cm–2. Si + O2 + 2H2O → Si(OH)4
Ecell = 2.091 V (xxvii)
The main challenges of Si-O2 cells are illustrated
within Figure 7.
In alkaline electrolyte there is a side reaction that
Another variation of a Si-O2 cell has also been increases with respect to basicity, Equation (xxviii):
considered in which the cell alternatively operates
in an alkaline electrolyte (37–40) with specific Si + 2OH– + 2H2O → SiO2(OH)22– + 2H2(xxviii)

Discharge

Anode e– Cathode
Problems of silicon Membrane required
•• Passivation of Si from e– – + •• To maintain optimal water
surface accumulation of content within electrolyte
Si(OH)4 or SiO2 O2 and to prevent the cell
•• Self-corrosion of silicon drying out
Si
“Si4+”
O2
Alkaline or Porous O2
ionic liquid carbon +
Si(OH)4
electrolyte catalyst
Modified or SiO2
Si surface

•• Optimise gas diffusion electrode for Si-O2 cell

Electrolyte •• Deactivation of catalyst by electrolyte
Limited Si(OH)4 solubility
in H2O 1.6
•• Si(OH)4 precipitate
1.4
blocking electrode pores
1.2

Cell 1.0
Voltage, V

•• Practical operating voltage

0.8
of 0.8–1.1 V
0.6

Rechargeability 300 mA cm–2 100 mA cm–2 50 mA cm–2 10 mA cm–2

0.4
26.7 mAh 15.25 mAh 12.5 mAh 3 mAh
•• Mechanical regeneration
0.2
of Si
0
0 100 200 300 400 500 600 700
Time, h
Fig. 7. Specific challenges facing the Si-O2 battery and cell performance data using EMI·(HF)2.3F
RTIL electrolyte at different constant current densities. Cycling data from figure reproduced from (41)
© Elsevier 2010

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https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

7. Zinc-O2 offers a tantalising glimpse of its great promise,

if the primary technology performance could be
With a theoretical specific energy of 1086 Wh kg–1 replicated in a secondary system. The principal
the Zn-O2 battery is one of the most studied disadvantage at present is the low cycle life of
metal-air systems offering low cost and relatively the cell when electrochemically recharged and a
abundant materials (zinc, potassium hydroxide, voltage gap (0.8 V under a load of 20 mA cm–2)
carbon, manganese dioxide) (3, 42). The battery between discharge and charge processes.
has an open circuit potential of 1.65 V in 6 M Rechargeable Zn-O2 suffers from two key
KOH and results from the elimination of the H2 drawbacks that do not affect the primary cell:
evolution reaction. This is due to the presence at the poor stability of the air cathode when used to
the surface of the Zn metal electrode, of a thin charge the battery, and as in the earlier example
ionically conducting, but electronically insulating of lithium metal, the formation of dendrites
layer of ZnO. Water is therefore excluded from on the zinc anode leading to short circuits and
the electrochemical interface, thus the effective shedding of zinc. Dendrite formation occurs as
stability range of the electrolyte is extended the Zn is replated from an electrolyte containing
(Equations (xxix)–(xxxi)): non-uniform zincate, Zn(OH)42– composition
Anode: gradients and uneven ZnO at the surface.
Gravitational demixing causes the concentration of
Zn + 4OH– Zn(OH)42– + 2e–
zincate ions to increase at lower positions, resulting in
Ea = –1.199 V vs. SHE (xxix)
slight differences in the conductivity of the electrolyte.
In solution: Consequently there is a gradual redistribution of
the zinc, so that the lower portions of the electrode
Zn(OH)42– ZnO + 2OH– + H2O(xxx)
become thicker as it is stripped and plated.
Air cathode: Rechargeable Zn-O2 cells require zinc precipitation
from the water-based electrolyte to be closely
O2 + 2H2O + 4e– 4HO–
controlled. Challenges include dendrite formation,
Ec = 0.401 V vs. SHE (xxxi)
non-uniform zinc dissolution and limited solubility
Leading to the overall reaction, Equation (xxxii): in electrolytes. Electrically reversing the reaction at
a bifunctional air cathode, to liberate oxygen from
Zn + 1/2O2 → ZnO Ecell = 1.6 V (xxxii)
discharge reaction products, is difficult; membranes
Zn is easily recyclable, thereby offering both a tested to date have low overall efficiency. Charging
sustainable and low toxic energy storage device. voltage is much higher than discharge voltage,
The recycling process is as follows: producing cycle energy efficiency as low as 50%.
1. disassembly of the used Zn source (typically Providing charge and discharge functions by
80% Zn utilisation) separate unifunctional cathodes increases cell size,
2. reaction of the Zn anode oxidation product weight and complexity.
(ZnO) with the electrolyte (KOH), Equation A satisfactory electrically recharged system
(xxxiii): potentially offers low material cost and high
specific energy. Figure 8 summarises the main
ZnO + 2KOH + H2O → K2Zn(OH)4 (xxxiii)
characteristics and challenges of a Zn-O2 cell and
3. electrowinning of the zincate solution, Equation shows the charge-discharge cycles of a cell with
(xxxiv): a hierarchical meso-macroporous lanthanum
manganite (LaMnO3) cathode at 25 mA cm–2
K2Zn(OH)4 → Zn + 2KOH + H2O + ½O2 (xxxiv)
current density (43).
4. reassembly of the Zn source containing the There has been a recent increase in interest
electrowon Zn. in rechargeable Zn-air with a number of studies
Millions of primary Zn-O2 (Zn-air) batteries are reported. In particular, Wu et al. (44) used a
sold annually for hearing aids and other medical simple scalable procedure to manufacture porous
devices. Commercially available cells can have bifunctional electrodes for the Zn-O2 battery.
very high specific energies and energy densities, The polyhedral carbon electrodes reported use a
up to 442 Wh kg–1 and 1672 Wh dm–3 respectively Zn-doped Co-based zeolitic imidazolate frameworks
for the Duracell® Zn-air button cell. The primary (ZnCo-ZIFs) precursor. The authors state that
Zn-air cell is a mature technology, which is not Zn doping produces small Co nanoparticles with
currently the case for rechargeable Zn-O2 and high nitrogen content that enhances both the

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https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

Discharge

e–
Anode Cathode
Problems of zinc e –
– + •• Low cycle energy efficiency as low
•• Dendrite formation as 50%
•• Deformation of 4OH– 2OH– •• Large voltage gap of 0.8 V at
electrode from current loads of 20 mA cm–2
gravitational demixing Membrane required
Zn Zn(OH)42– O2
•• Blocking CO2 whilst allowing O2 to
ZnO + 2OH–
pass
H2O •• To maintain optimal water content
+ H2O
within the electrolyte and prevent
Alkaline Porous the cell drying out
Electrolyte electrolyte carbon +
•• Formation of Zn(CO3)2 from catalyst
CO2 ingress
•• Cell drying out from water 3.0 O2
evaporation
CO2
2.5
Cell voltage, Ecell, V

2.0 Cell
•• Voltage gap >1.5 V
1.5 •• Large overpotential
required for OER

1.0
Zn/O2, ±25 mA cm–2 charge/discharge, 600 s

0.5
0 500 1000 1500 2000 2500 3000
Time, s

Fig. 8. Challenges and performance for rechargeable Zn-O2. Charge, discharge cycle figure reproduced from
performance curve data from (43) © Elsevier 2014

evolution and reduction of oxygen. The ZnCoNCx hysteresis between 0.6–1 V at 10–20 mA cm–2.
materials are highly graphitised with a porous These include transition metal hydroxysulfides
polyhedral structure and large surface area. The (46), pyrolysised MOFs containing Zn and Co
authors reported a cell able to cycle up to 100 (47), Fe3Mo3C-supported IrMn Clusters (48),
times at 7 mA cm–2 with only 10 mV difference Ni3FeN-supported Fe3Pt intermetallic nanoalloys
between charge and discharge cycles. In another (49), CoO0.87S0.13 (50), carbon nitrides (51) and
example, a composite material consisting of Co3O4 Fe0.1Ni0.9Co2O4 spinels ­(52).
nanoparticles decorated with carbon nanofibers
(CNFs) was used as a bifunctional electrode for
8. Iron-O2
the Zn-O2 battery. Metal ion containing polymers
were electrospun and carbonised to obtain the Alkaline Fe-O2 batteries were under intense
composite. The authors claimed that the electrode industrial investigation during the 1970s and
was able to yield four electrons during the reduction early 1980s, most notably by The Westinghouse
of oxygen, competing with commercial platinum Electric Corporation, USA, and the Swedish
electrodes, and that the prototype cell had an National Development Corporation, Sweden, for
energy efficiency of 64% when charged/discharged the application of an electric vehicle battery. The
at 1 mA cm–2 (45). alkaline Fe-O2 battery has a predicted open circuit
Recent reports have shown greatly improved cell voltage of about 1.28 V and a theoretical
cyclability under ambient conditions, with 100+ specific energy of 764 Wh kg–1 with the formation
cycles being routinely presented. A number of of Fe(OH)2 (53).
catalysts have shown bifunctionality in order Iron electrodes have been used for over 70 years in
to overcome the sluggish kinetics of the oxygen Ni/Fe batteries, and the notable advantages of this
evolution reaction (OER) and ORR with voltage system are the availability, abundance and low cost

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https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

of iron. Iron electrodes are fabricated into sintered anodic dissolution reaction, poor low-temperature
structures. The iron electrode is formed from high performance, and low charge acceptance at high
purity iron oxide powder in order to increase the ambient temperatures due to a parasitic HER. The
overpotential for H2 evolution. However, this adds challenges and performance of a Fe-O2 cell are
significant cost to electrode fabrication. The Fe-O2 shown in Figure 9.
battery substitutes the nickel electrode for an air More recently a solid electrolyte based Fe-O2 cell
breathing electrode which in theory could increase has been reported (56, 57). An oxide ion conductor
the specific energy by 100%. is employed as the electrolyte and the cell operates
The reactions at the anode are complex and at temperatures greater than 600°C. The solid
still a matter of discussion and involve several oxide iron-air battery utilises the FeO-Fe phase
intermediates. The reaction is also complicated by equilibrium as a means of storing electrical-chemical
hydrogen evolution if the metallic iron corrodes to energy via a series of H2/H2O-mediated reversible
Fe(II), forming Fe(OH)2, and the electrode gradually electrochemical-chemical looping reactions. The
becomes coated with a film of Fe(OH)2 as a result of capacity and efficiency characteristics of this
the following reactions, Equations (xxxv)–(xxxviii): battery were found to be strongly dependent
on the degree of iron utilisation: higher charge
Fe → Fe2+ + 2e– E° = –0.447 V vs. SHE (xxxv)
and energy storage capacity, but lower round-
trip efficiency, can be produced at higher iron
Fe + 2OH– Fe(OH)2 + 2e–
E° = –0.88 V vs. SHE (xxxvi) utilisation, and lower charge and energy storage
capacity, but higher round trip efficiency, can be
2H2O + 2e– → 2OH– + H2 produced at lower iron utilisation.
E° = –0.8277 V vs. SHE (xxxvii) A bifunctional carbon based air electrode containing
0.5 mg cm–2 loading of 30% palladium on carbon,
Total reaction: reported by McKerracher et al. (58), was stable after
1000 charge/discharge cycles at 10 mA cm–2 in an
Fe + 2H2O → Fe(OH)2 + H2(xxxviii)
Fe-O2 alkaline battery. At higher current densities
If the HER, Equation (xxxviii), can be avoided (20–80 mA cm–2), the electrode showed better
the efficiency of the Fe-O2 battery is greater. The performance than some commercially produced
formation of Fe(OH)2 is followed by oxidation to platinum on carbon gas diffusion electrodes. The
Fe(III) forming magnetite, Fe3O4, Equation (xxxix): authors suggested that the better performance is
due to the well-dispersed, nanoscale Pd particles.
3Fe(OH)2 + 2OH– Fe3O4 + 4H2O + 2e–
Figueredo-Rodríguez et al. (59) reported an Fe-O2
Ea = –0.76 V vs. SHE (xxxix)
battery with a specific energy of 764 W h kg−1 Fe
The reaction at the cathode is the reduction of and 453 W h kg−1 Fe energy density with a charge
oxygen, Equation (xl): capacity of 814 mA h g−1 Fe when it was cycled at a
current density of 10 mA cm−2. The cell employed
½O2 + H2O + 2e– → 2OH–
nanocomposite iron electrodes manufactured by
Ec = 0.401 V vs. SHE (xl)
iron oxide synthetised via a molten salt fusion
The overall reaction where magnetite (as method followed by mixing with a high surface area
opposed to Fe(OH)2) is the discharge product is carbon by ball milling. The gas diffusion electrodes
Equation (xli): comprised three main parts bound together by hot
pressing at 180°C and 250 kPa:
3Fe + 2O2 → Fe3O4 Ecell = 1.15 V (xli)
1. a gas diffusion layer composed of 80 wt% high
The manufacturing of the iron electrode involves surface area (ca. 64 m2 g−1) carbon mixed with
additives such as bismuth and sulfur to minimise 20 wt% polytetrafluoroethylene
the corrosion of the iron electrode and the evolution 2. a catalyst layer formed by 30 wt% Pd/C catalyst
of hydrogen in an attempt to favour Equations in a 5 wt% Nafion solution, and
(xxxix) and (xl). The formation of magnetite Fe3O4 3. an expanded nickel mesh current collector.
Equation (xli) leads to a lower cell voltage.
Problems that adversely affect the performance
9. Conclusion
of the iron anode are spontaneous corrosion
in the charged state (leading to a high rate of Modern society requires energy storage devices
self-discharge), a low faradaic efficiency for the with much higher levels of energy storage than

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https://doi.org/10.1595/205651318X696729 Johnson Matthey Technol. Rev., 2018, 62, (2)

Discharge

Anode e– Cathode
Problems of iron •• Low cycle energy efficiencies,
•• Parasitic corrosion of Fe e– – + as low as 40%
resulting in H2 evolution •• Large voltage gap of 0.8 V at
•• Fe(OH)2 precipitate on 6OH– 8OH– current loads of 25 mA cm–2
surface
•• Low faradaic efficiency for
anode dissolution reaction Fe
3Fe(OH)2 O2
+2OH–

Fe3O4+ 4H2O 4H2O

Alkaline Porous
electrolyte carbon +
catalyst
Electrolyte
1.8
•• Cell drying out from water
evaporation
1.6

Cell
Cell voltage, Ecell, V
1.4 (a) (b)
•• To maintain optimal water
content within electrolyte and 1.2
to prevent the cell drying out
1.0

0.8
Charge 25 mA cm–2
0.6
Discharge 30 mA cm–2
Charge/discharge at + 40 mA cm–2
0.4
0 2 4 6 8 10 12 14 16 18
Time, h

Fig. 9. Challenges and performance for Fe-O2 and comparison of two charge-discharge cell potential curves
for an Fe-O2 battery: (a) 25 mA cm–2 charge discharged at 30 mA cm–2 of a prototype stack containing
190 air and 95 iron electrodes of 10 × 20 cm divided into 19 cells connected in series (54); (b) charge and
discharge at 40 mA cm–2, the cell contained air electrodes of 100 cm2 area separated by 3–4 mm from the
Fe electrode (55). Performance curve data provided by C. Ponce de Leon

ever before. Rechargeable metal-O2 cells are a cell is not proof of true reversibility. Major gaps
amongst the few contenders that can exceed in fundamental knowledge of all types of metal-O2
the stored energy of the current state-of-the-art cells remain, for example the realisation of
Li-ion cells. Multivalent metal-air (O2) batteries electrolyte and materials composition that provide
described herein possess significant promise for reversible stripping and plating of metal anodes
high energy storage applications, but in general and reversible oxide/hydroxide production and
most examples (with the exception of primary decomposition. As a result, much ground-breaking
zinc-air that has been commercialised for several and exciting science remains to be done.
years) are a long way from being a technological
product. Fundamental challenges in all aspects of
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The Authors
Laurence Hardwick is Professor of Electrochemistry and Director of the Stephenson
Institute for Renewable Energy within the Department of Chemistry at the University
of Liverpool, UK. His research interests focus on understanding reaction mechanisms
of metal-air batteries and the development of surface sensitive in situ electrochemical
Raman and infrared spectroscopies to probe battery electrode-electrolyte interfaces.

Carlos Ponce de León Albarrán is Senior Lecturer, Energy Technology Group within
Engineering and the Environment at the University of Southampton, UK. He is working
from an electrochemical engineering perspective in aqueous metal-air batteries,
water treatment, metal ion removal, characterisation of novel electrode materials,
electrochemical strategies for pollution control and redox flow cells for energy
conversion.

149 © 2018 Johnson Matthey