Journal of Power Sources xxx (xxxx) xxx

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Review article

Innovative zinc-based batteries

Niklas Borchers a, b, 1, Simon Clark c, 1, Birger Horstmann a, b, *, Kaushik Jayasayee c, Mari Juel c,
Philippe Stevens d, **
a
German Aerospace Center (DLR) Institute for Engineering Thermodynamics, Pfaffenwaldring 38-40, 70569, Stuttgart, Germany
b
Helmholtz Institute Ulm (HIU), Helmholtzstr. 11, 89081 Ulm, Germany
c
SINTEF Industry, New Energy Solutions, Sem Sælands Vei 12, 7491 Trondheim, Norway
d
Electricité de France (EDF), R&D Division, LME Departement, 7 Avenue des Renardières, 77818 Moret sur Loing Cedex, France

H I G H L I G H T S

• Presenting recent innovations in the field of zinc based rechargeable batteries.

• Reviewing development status, challenges, and promising research directions.
• Addressing research on zinc metal anodes in various electrolytes.
• Highlighting advances in rechargeability of zinc-air cells and promising concepts.
• Discussing cell chemistries and charge storage mechanisms for zinc-ion batteries.

A R T I C L E I N F O A B S T R A C T

Keywords: The demand for high-performance, affordable, and safe energy storage solutions is growing, driven in part by the
Zinc-air batteries incorporation of fluctuating electricity sources like wind turbines and solar cells in the electric grid. Batteries
Zinc-ion batteries offer such a storage solution in both distributed systems such as households and large-scale industrial systems.
Zinc metal electrode
The quest for more resource-efficient alternatives to lithium-ion batteries is on its way to meet the increasing
Aqueous electrolyte
demand. Zinc batteries are particularly ecologically friendly due to their use of abundant raw materials and their
facile recyclability. High energy densities add to the benefits of this technology. These advantages stem from the
use of zinc metal electrodes in combination with effective and affordable aqueous electrolytes. Zinc battery types
are distinguished by their cathode materials and electrolytic charge carriers. Zinc-air batteries work with oxygen
from air and have the potential to offer the highest energy densities. Zinc-flow batteries could enable large scale
battery storage. Zinc-ion batteries are a more recent development which promise large power densities and long
cycle lives. In this review, these technologies are discussed in detail. We summarize the development status of
each technology, criticize typical deficiencies of current studies, discuss technological challenges, and highlight
promising future research directions.

1. Introduction Large volume battery manufacturing (Gigafactories), major research

Electrochemical energy storage is regarded as a key technology for
stabilizing the electricity system in the carbon-neutral future. Batteries
are a solution for the growing energy storage demand, both for mobile
and stationary applications. From a global perspective, it will be crucial
that next-generation batteries are made of non-toxic and abundant raw
materials with a high potential for reuse and recycling.
and development efforts, and steady progress in performance have
brought the cost of lithium-ion batteries down to very competitive levels
which has made it among the most popular battery chemistries today.
This has enabled lithium-ion batteries to become the most obvious so­
lution to electricity storage in almost all applications, from the internet
of things (IoT) to portable, mobile, and stationary applications. How­
ever, despite their numerous advantages, lithium-ion batteries also have

* Corresponding author. German Aerospace Center, Pfaffenwaldring 38-40, 70569 Stuttgart, Germany.
** Corresponding author.
E-mail addresses: birger.horstmann@dlr.de (B. Horstmann), philippe.stevens@edf.fr (P. Stevens).
1
These authors have contributed equally to this work.

https://doi.org/10.1016/j.jpowsour.2020.229309
Received 6 November 2020; Received in revised form 23 November 2020; Accepted 29 November 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Niklas Borchers, Journal of Power Sources, https://doi.org/10.1016/j.jpowsour.2020.229309
N. Borchers et al.
limitations. The organic electrolyte is highly flammable and at risk of
thermal runaway. The current generation of lithium-ion batteries often
contains critical raw materials, whose supply may become strained in
the future [1].
Zinc-based batteries are a prime candidate for the post-lithium
era [2]. Fig. 1 shows a Ragone plot comparing the specific energy and
power characteristics of several commercialized zinc-based battery
chemistries to lithium-ion and lead-acid batteries. Zinc is among the
most common elements in the Earth’s crust. It is present on all conti­
nents and is extensively produced worldwide at affordable prices [3].
Zinc-based batteries also have the potential to use lower-cost
manufacturing techniques since they do not need special dry room
conditions. Zinc and zinc oxide are easy to recycle by either electro­
chemical, chemical, or thermal processes. The recycling of zinc-based
batteries is already established and commercialized for primary zinc
batteries.
Zinc batteries have a long history, with the first scientific papers on a
Zn–Cu battery dating back over 200 years [5]. Although already widely
distributed as primary batteries (alkaline and saline zinc-carbon batte­
ries, zinc-air button cells, etc.), rechargeable zinc batteries have strug­
gled to reach widespread commercialization. However, a modern wave
of start-up companies is promoting the technology, particularly for
stationary applications.
The key advantage of zinc batteries is the stability of zinc metal
electrodes in aqueous electrolytes which provide a large theoretical
capacity (819.7 mAh∙g-1, 5847.2 mAh∙cm-3). Hydrogen evolution is
thermodynamically possible on zinc metal, but it can be kinetically
suppressed. This allows cell voltages higher than the theoretical stability
window of water. Aqueous electrolytes offer not only low costs and high
intrinsic safety but also a versatile toolbox for design adjustments. New
electrolytes are being explored for zinc-air and zinc-ion batteries to
make cells that work in near-neutral pH conditions. At an even lower
technology readiness level (TRL), the zinc-ion battery also has its
organic electrolyte family [2].
The development of rechargeable zinc batteries has long focused on
chemistries like zinc-air, nickel-zinc, and zinc-flow batteries. Zinc-air
batteries are open to the air and utilize the reaction of zinc with oxy­
gen to zinc oxide. Strongly alkaline electrolytes support this cell reaction
and provide fast ionic transport. The oxygen redox chemistry enables the
high energy densities that metal-air batteries are known for but poses
challenges for long-term stability [6]. Aqueous zinc-ion batteries that
use Zn2+ intercalation cathodes have recently gained more attention as
Fig. 1. Ragone plot illustrating the energy and power characteristics of several Zn-
based cell chemistries (alkaline zinc-MnO2, zinc-air, nickel-zinc, and silver-zinc).
Legacy lead-acid and present lithium-ion systems are included for comparison.
Reprinted from Ref. [4] with permission from Elsevier.
2
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potential candidates for low cost and safe storage. The closed-cell design
improves cycle life. Mildly acidic electrolytes allow the shuttle of zinc
between the electrodes, favoring high power densities [7].
This review focuses on rechargeable zinc battery chemistries that
have generated recent innovations or taken steps towards commercial­
ization. Fig. 2 provides an overview of the working principles for the
main aqueous zinc-based chemistries discussed in this work. First, open
zinc cells – in which some mass transport through the main reaction
chamber occurs – including zinc-air (Fig. 2a) and zinc-flow (Fig. 2c and
d) batteries are discussed. Then the discussion shifts to closed zinc
batteries, including nickel-zinc and zinc-ion (Fig. 2b) chemistries.
Within this work, the different open and closed material systems are
consistently compared considering the fundamental electrode reactions,
design goals, current research topics, and commercialization trends.
2. Zinc metal electrodes
Zinc metal is a versatile, high-energy, and low-cost electrode mate­
rial. These advantages have made zinc metal electrodes appealing for a
wide range of battery chemistries like zinc-air, zinc-ion, and zinc-flow
batteries, shown respectively in Fig. 2. Each of these battery chemis­
tries has different design considerations which should be reflected in the
zinc electrode and electrolyte. For example, zinc-air batteries are
designed to sequester zinc as zinc oxide precipitated in the anode. In this
case, the controlled precipitation of ZnO is desirable. On the other hand,
zinc-ion batteries are designed to transport zinc ions across the cell to be
intercalated into the cathode material. In this case, the precipitation of
ZnO or any zinc salt is undesirable. Achieving these design goals is
determined in large part by the selection of an appropriate electrolyte
composition, combined with engineering of the zinc electrode archi­
tecture and surface properties.
Zinc metal electrodes are strongly influenced by the electrolyte
environment in which they operate. Traditionally, most commercial zinc
electrodes have been used in combination with concentrated alkaline
electrolytes like KOH or saline near-neutral electrolytes like ZnCl2 or
NH4Cl. Today, new zinc-based cell chemistries like zinc-ion are also
pursuing the use of near-neutral electrolytes like ZnSO4.
Fig. 3 shows a Pourbaix diagram, indicating the equilibrium prop­
erties of a simple Zn–H2O system. In aqueous media, the mechanism and
equilibrium potential of the zinc electrode reaction depend on both the
pH and the composition of the solution [8,9]. In acidic and near-neutral
electrolytes, the zinc electrode reaction is:
Zn ​ ⇌Zn2+ + 2 e− , E0 = − 0.762 V (1)
2+
The dissolved Zn ions are solvated by water or form complexes
with other dissolved species. For example, the dominant complex in
solutions of zinc chloride is tetrachlorozincate, ZnCl2- 4 . As shown in
Fig. 3, zinc is very soluble in acidic solutions, which enables highly
concentrated electrolytes to be used. Zinc solubility is reduced in near-
neutral media, which can lead to the precipitation of mixed Zn salts
depending on the composition of the electrolyte. For example, zinc hy­
droxide chloride (Zn5(OH)8Cl2) may precipitate from chloride-
containing solutions, and zinc hydroxide sulfate (Zn4(OH)6SO4) may
precipitate from sulfate-containing solutions. In zinc-ion batteries, zinc
salt precipitation is unwanted and leads to self-discharge and perfor­
mance degradation.
In alkaline media, the zinc electrode half-cell reaction is:
Zn + 4 OH− ⇌Zn(OH)2−4 + 2 e− , E0 = − 1.199 V (2)
Electrochemical oxidation of Zn to Zn(OH)2-
4(zincate) in alkaline
media tends to produce oversaturated zincate solutions [10]. When the
concentration of zincate surpasses a critical saturation limit, a solid
phase dominated by ZnO precipitates.
​ Zn(OH)2−4 ⇌ZnO + H2 O + 2 OH− (3)
N. Borchers et al.
Fig. 2. Schematic of the main elements and half-cell reactions in (a) zinc-air batteries with strongly alkaline KOH electrolyte, (b) zinc-ion batteries with mildly acidic
ZnSO4 electrolyte, and zinc flow batteries based on (c) systems in which energy and power are decoupled and (d) systems in which energy and power are coupled.
Fig. 3. Pourbaix diagram of a simplified Zn–H2O system at [Zn]T = 1 M. The
dashed lines indicate the potentials of the OER and HER. The potential of the
zinc electrode is calculated from the electrolytic concentration of Zn2+.
In zinc-air batteries, the precipitation of ZnO is important because it
enables the cell to reach a stable working point and achieve the high
energy density that makes it an attractive battery chemistry. However,
the precipitation of ZnO creates a passivation layer over the electrode
surfaces that acts as a barrier to species transport between the electrode
and the electrolyte. During charge, dissolved Zn2+ species in the elec­
trolyte are consumed to produce zinc metal, which in turn drives the
dissolution of precipitated phases which have stored zinc active
material.
It is important to note that the selection of electrolyte pH and
composition can fundamentally alter the design principle of the zinc
electrode. In alkaline batteries, the goal is to limit the transport of
3
Journal of Power Sources xxx (xxxx) xxx
aqueous zinc species in the electrolyte and locally precipitate ZnO. In
this case, OH− is the charge carrier between the half-cells. In mildly
acidic zinc-ion batteries, the goal is to support the transport of zinc
species through the electrolyte to the cathode while avoiding all types of
zinc salt precipitation. In this case Zn2+ is the charge carrier between the
half-cells.
2.1. Challenges
2.1.1. Corrosion
Zinc metal is thermodynamically unstable in water, particularly at
lower pH values, which reduces the coulombic efficiency (CE) and can
cause the electrode to undergo a parasitic self-discharge reaction to
produce H2 gas:
In acidic media Zn + 2 H+ →Zn2+ + H2 (4).
In alkaline media Zn + 2 H2 O + 2 OH− →Zn(OH)2− 4 + H2 (5).
The evolution of H2 gas is of particular concern in closed cells, where
the increase in pressure can cause mechanical deformation of the cell. A
recombination catalyst to consume the H2 produced is sometimes added
inside the top of the cell [11].
Beyond these practical cell design challenges, the HER side reaction
also poses a problem for research. Lab-scale research cells often use zinc
foil electrodes due to their simplicity and easily reproducible results.
However, the low surface area of zinc foil cells increases the local cur­
rent density seen by the surface and can accelerate the HER. This side
reaction, occurring at the same time as the zinc electrode reaction, may
subtly impact the observed electrochemical performance [12].
There are two approaches to deal with the challenge of zinc electrode
corrosion: (i) suppressing the kinetics of the HER through alloys or ad­
ditives and (ii) limiting the exposure of the surface to water through
coatings or electrolyte engineering.
N. Borchers et al.
2.1.2. Passivation
When the concentration of dissolved zinc species surpasses the
saturation limit, solid products precipitate in the cell. In alkaline elec­
trolytes, the solid product is ZnO, while in near-neutral electrolytes the
solid product may comprise a variety of solids depending on the elec­
trolyte composition. For example, Zn5(OH)8Cl2 can precipitate in near-
neutral electrolytes containing chloride salts, and Zn4(OH)6SO4 can
precipitate in near-neutral electrolytes containing sulfate salts [13].
Passivation in alkaline systems has been extensively investigated in the
literature and is the subject of a dedicated review by Bockelmann et al.
[14]. However, zinc electrode passivation in near-neutral electrolytes
remains less well understood.
The formation of solid films over the electrode surfaces acts as mass
transport barrier, hindering the exchange of chemical species between
the electrode and the bulk electrolyte. The severity of the passivation
effect is determined by the thickness and porosity of the precipitated
film as well as the magnitude of the local current density in the
electrode.
In alkaline electrolytes, the zinc passivation process is typically un­
derstood to occur in three steps [15,16]: (i) zinc dissolution, (ii) revers­
ible nucleation and growth of a porous zinc oxide film (Type I ZnO), and
(iii) irreversible formation of a dense zinc oxide layer (Type II ZnO).
When designing the zinc electrode, the reversible precipitation of porous
Type I ZnO is acceptable and even desirable to help achieve high energy
density. However, the formation of a Type II ZnO layer is deleterious to
electrode performance and can cause the sudden death of the battery.
Design approaches to control the formation of precipitated films in
zinc electrodes include the inclusion of additives to adjust the solubility
and engineering porous structures to contain the precipitated products.
2.1.3. Shape change and dendrite formation
Porous zinc electrodes can span thicknesses of the order of hundreds
of micrometers to a few millimeters. The conversion of the active ma­
terial does not occur homogeneously over the entire electrode volume,
rather zinc close to the separator interface tends to dissolve first with the
reaction zone moving into the bulk of the electrode as the discharge
proceeds. A combination of x-ray computed tomography [17–19] and
model-based research [20] have observed this effect. Although the
inhomogeneous dissolution of zinc is not a major concern in primary
batteries, it can lead to electrode shape change and degradation in
secondary batteries.
The solubility of zinc in aqueous solutions can vary from highly
soluble in acidic media to moderately soluble in alkaline media. The
solubility of zinc enables the transport of aqueous zinc species through
the electrolyte. While this may be an advantage for some zinc battery
chemistries (e.g. zinc-ion), it creates a situation in which zinc can
dissolve in one region of the electrode, diffuse some distance, and pre­
cipitate in a different region of the electrode. Over many charge and
discharge cycles this can lead to the redistribution of active material and
the shape change of the electrode [20].
Another equally severe form of shape change is the growth of
metallic zinc dendrites on the electrode surface during electrical
recharging. Dendrite formation is one of the major challenges hindering
the development of secondary zinc electrodes. If the dendrites growth is
large enough to contact the cathode, the resulting internal short-circuit
causes the cell to stop functioning. Fortunately, unlike lithium-ion bat­
teries, this has no other consequences other than a loss of performance
and does not lead to a fire risk.
A variety of indicators have been proposed to predict the tendency of
certain electrodes to form dendrites including the surface diffusion of
zinc atoms [21], critical zinc ion concentration at the
electrolyte-electrode surface [22], and the dominant orientation of zinc
crystal planes [23].
The predominance of certain crystal planes in electrodeposited zinc
structures has long been known to depend on factors like electrolyte
composition, substrate composition, and alloying elements [24,25].
4
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Some crystal planes are proposed to be more favorable for dendrite
formation than others [26]. For example, zinc growth in the (002) basal
plane maintains a low angle (0–30◦ ) alignment and is proposed to be
more resistant to dendrite formation than high angle (70◦ – 90◦ ) planes
like (100).
The mesoscale mechanisms of zinc dendrite nucleation, growth, and
dissolution are the subject of recent studies using advanced imaging
techniques including operando temporally resolved light microscopy
[27], high-resolution synchrotron x-ray computed tomography (SXCT)
and ex-situ FIB-SEM [28,29] (see Fig. 4). Detailed observation of
dendrite growth in alkaline media shows that dendrites nucleate on local
irregularities on the electrode surface where the local current density is
high, in agreement with model-based studies [30]. The rate of dendrite
growth is a function of the applied current density. The grown dendrites
tend to be narrow at the base and grow larger towards the top. As a
result, dendrites can break loose from the electrode and become elec­
trochemically inactive (shedding). When the electrode is discharged, the
inhomogeneous dissolution of the zinc dendrites can also contribute to
their collapse and detachment from the electrode surface. Upon
recharging, new dendrites form on the electrode surface and form an
entangled network with the remnants of the pre-existing dendrites. This
can lead to a significant increase in the electrode surface area between
charging-discharging cycles and modify the properties of the electrode.
The observed zinc morphologies match the simulations of diffusion
limited dendrite growth [31].
There are a variety of proposed methods in use to limit electrode
shape change and dendrite growth. They include: (i) tuning the elec­
trolyte saturation properties through the use of additives and/or elec­
trode structure modifications, (ii) encouraging the growth of
preferentially oriented zinc phases through dopants on the surface or
electrodeposition on a suitable substrate, and (iii) cell-level counter­
measures like pulse-charging protocols or forced convection of the
electrolyte. Zinc redox flow batteries manufactures have treated this
issue by performing full discharge cycles regularly to completely strip
the electrode from any metallic zinc to restart with a “fresh” negative
electrode [32,33].
2.2. Progress
2.2.1. Zinc alloys and additives
In commercial zinc-based batteries, the zinc electrode is often
alloyed, doped, or mixed with additives to help improve performance by
suppressing gas evolution or facilitating precipitation of solid discharge
products.
Gas evolution is a surface phenomenon occurring at the electrode-
electrolyte interface. Dispersing corrosion inhibitors throughout the
bulk of the zinc material can help to maintain corrosion protection as the
electrode is discharged, but to be effective in rechargeable batteries, the
inhibitors must remain at the surface when the electrode is charged.
Since the early commercialization of zinc-based batteries, it has been
known that amalgamation of zinc metal can suppress the kinetics of the
HER [34,35]. However, the use of mercury has been phased out due to
environmental and toxicity concerns. Today, commercial zinc electrodes
can feature ppm quantities of dopants including indium, bismuth, or
aluminum [36]. Current research seeks to better understand the corro­
sion suppression mechanism and identify zinc alloys and dopants that
retain their surface properties after recharging in different electrolyte
solutions [37].
Zinc-indium alloy electrodes show lower corrosion currents and
higher HER overpotentials compared to pure zinc in both alkaline [38,
39] and near-neutral solutions [40]. Combining DFT calculations with
differential electrochemical mass spectrometry (DEMS) measurements,
Lysgaard et al. showed that zinc electrodes doped with In generated
significantly less H2 gas during cycling process compared to un-doped
zinc foil, and that In is thermodynamically favored to remain on the
surface after recharging [38]. They also found that co-doping Bi together
N. Borchers et al.
Fig. 4. Operando Study of Zinc Dendrite Growth at 15 mA/cm2 in the Cell without Separator (A–H) Zinc dendrite growth after (A) 180 s, (B) 720 s, (C) 860 s, (D) 1020 s,
and (E) 1200 s 3D analysis of zinc dendrites: (F) 3D reconstructed tip, (G) 3D reconstructed image of dendritic cluster, (H) 3D reconstructed single dendrite. The table shows the
dendrite volume, surface, and volume-specific surface. Reprinted from Refs. [29] with permission from Elsevier.
with In had the effect of suppressing H2 evolution even further. Attrib­
uting the observed reduction in H2 gas evolution to the weaker
adsorption of hydrogen on In + Bi co-doped surfaces, their study offers
theory-based guidance on the selection of zinc electrode dopants.
Another approach to improving zinc electrode performance is to
blend the zinc metal with other solid additives to form composite elec­
trodes, either through physical mixing or chemical co-precipitation. The
most basic example of this is the initial inclusion of ZnO in the electrode
to remove the nucleation barrier for precipitation and stabilize the
discharge potential [41]. Another popular additive is calcium hydroxide
which traps zinc ions in the form of calcium zincate which is less soluble
than ZnO and provides a source of zinc ions in proximity to the zinc
electrode [42–44]. Zincate ions produced from the zinc electrode on
discharge reacts with the calcium hydroxide to form insoluble calcium
zincate. When the zinc electrode is charged, the calcium zincate present
releases zincate ions in the vicinity of the zinc as the local zincate con­
centration drops due to its consumption.
2.2.2. Zinc electrode coatings
The application of coatings to the zinc electrode surface offers an
additional tool to help mitigate the HER and formation of dendrites.
Coatings include In Ref. [45,46], TiO2 [47–49], CaCO3 [50], bismuth
oxide [51], bismuth-doped silica [52], anion exchange ionomers [53,
54], reduced graphene oxide [55], and artificial SEIs [56,57].
Indium has long been investigated as an alloying element to help
suppress the HER, as discussed in the previous section. Recently, similar
approaches by Han et al. [45] and Hu et al. [46] suggest that coating the
zinc surface with a continuous indium film can fulfil dual requirements
for both HER and dendrite suppression. According to Han et al. the
adsorption energy of zinc atoms on an indium substrate is higher than on
a zinc substrate leading to the preferential deposition of Zn on In rather
than on Zn. They propose that the deposition of Zn on In could ensure a
more homogeneous Zn surface distribution. SEM characterization and
EDS mapping of the In-coated zinc foil electrodes confirm that In re­
mains on the surface after 100 discharge-charge cycles. Hu et al. suggest
that the coating creates a potential gradient to induce zinc to deposit
underneath the layer. Both studies investigate their proposed coatings in
ZnSO4 electrolytes, and both show a marked improvement in gas evo­
lution and the homogeneity of zinc plating.
Titanium dioxide has been proposed as a corrosion suppressive
coating for Zn and ZnO electrodes due to its electrochemical stability
and conductivity. In alkaline zinc-nickel batteries, Lee et al. reported
that coating ZnO with TiO2 via the sol-gel method at low annealing
5
Journal of Power Sources xxx (xxxx) xxx
temperatures supports the formation of a favorable anatase TiO2 surface
layer that reduces corrosion and zinc dendrite formation compared to
non-coated ZnO [48]. However, Lee et al. also found that annealing at
high temperatures (800 and 900 C), the coating is converted into
○
Zn2TiO4 through rutile TiO2 and ZnTiO3 phases. The resulting phase has
high crystallinity and low conductivity. Zhao et al. used atomic layer
deposition (ALD) to create an ultrathin TiO2 layer on zinc foil [49]. After
optimizing the thickness of the protective layer, the TiO2-coated elec­
trode demonstrated superior cycling performance in a zinc-MnO2 bat­
tery with Zn(SO3CF3)2 + Mn(SO3CF3)2 electrolyte. Zhang et al. recently
proposed coating ZnO nanorods with TiO2 as a solution to suppress the
HER and demonstrated the electrode in an alkaline zinc-nickel battery
[47]. Their study indicated high coulombic efficiency at a low electro­
lyte volume to discharged capacity ratio. Although their demonstrated
electrode does not show the appropriate areal capacity for practical
batteries, it is a proof-of-concept for future development.
2.2.3. Preferential orientation
Metallic zinc has a hexagonal close-packed (hcp) crystal structure,
with each atom coordinated to 6 nearest-neighbors. The (0001) plane
has the lowest surface energy (0.33 J∙m− 2) [58]. As a result, electro­
deposited zinc tends to initially form hexagonal platelets [59] and grow
into boulder, mossy, heavy spongy, dendritic or layered structures [60,
61]. Electrode-electrolyte systems and operating protocols that facilitate
platelet orientation parallel to the substrate with epitaxial growth in the
basal plane tend to show longer cycle life, while electrodes that favor
random platelet growth perpendicular to the substrate tend to show
reduced cycle life [23,59,62].
The composition and concentration of the electrolyte, structure of
the electrode, and the electrochemical operating protocol are all known
to influence the zinc morphology [60]. Different methods have been
proposed to help control the growth of deposited zinc metal in the
preferred orientation, including pulse-charging [63], additives, and
substrate engineering [64].
The growth of electrodeposited zinc is known to strongly depend on
the applied current density and local concentrations at the electrolyte-
electrode interface [65]. While the growth process is epitaxial for low
current density in alkaline and dilute sulfate solutions [66,67], the
application of high current density can lead to the nucleation and
growth of dendritic structures. By applying high current pulses [63], the
availability of zinc species can be tuned in a way that the zinc is
compactly deposited. If dendrites are already present on the electrode
surface, a recently proposed electro-healing protocol suggests that
N. Borchers et al.
cycling for a few cycles at a lower current density will preferentially strip
zinc from the dendrites [68]. After dissolving the dendrites, plating at
low current density can smooth the zinc surface and enable the shift
back to high current density operation, thus significantly improving the
lifespan of the zinc electrode.
It is important to note that the conditions favoring the formation of
smooth zinc deposits are complex, and there is not a one-size-fits-all
solution for all zinc electrode-electrolyte systems. For example, Glatz
et al. recently studied zinc deposition in highly concentrated mildly
acidic aqueous electrolytes relevant for zinc-ion batteries [69]. They
found that contrary to expectations, the cycle life of a zinc electrode in 3
M ZnSO4 was dramatically improved by cycling at higher current den­
sities. Fig. 5 shows SEM images of the zinc electrode surface after
charging the electrode for 1 mAh at different current densities. Charging
at 1 mA leads to randomly oriented platelets, while increasing the
applied current density to 10 and 20 mA favors the formation of stacked
basal plane layers. In this experiment, the total charge transferred was
kept constant at 1 mAh for each current density. The authors found that
keeping the time constant at 1 h with variable total charge capacity led
to the formation of similar random platelets also at higher current
densities. This finding may offer further guidance for the development of
pulse charging or high-rate protocols in zinc-ion batteries with
concentrated sulfate electrolytes [70].
The influence of the substrate on the preferential orientation of zinc
metal is the subject of recent research. Zheng et al. identify a set of se­
lection criteria for choosing a substrate that facilitates epitaxial growth
of zinc metal [59]. They noted that graphene is a promising substrate
due to its small lattice mismatch with the (0002) zinc plane and elec­
trochemical stability. Despite the challenges creating a macroscopic
electrode with the correct graphene orientation, the proposed solution
demonstrates improved cycle life and coulombic efficiency over both
zinc foil and zinc deposited on stainless steel. They propose Co and Ti as
alternative substrates to support epitaxial zinc growth. Other studies
investigating similar efforts to control the zinc growth on substrates
including Ni [71] and Cu [72] are reported.
Creating preferential zinc plane orientations can also be facilitated
by both organic and inorganic additives in the electrolyte. The use of
indium sulfate, tin oxide, and boric acid dissolved in an electroplating
Fig. 5. Morphology of the cycled zinc electrode in 3 M ZnSO4 electrolyte. (a) Pristine zinc foil surface and the zinc foil anode cycled at (b) 1 mA cm− 2, (c) 2 mA cm− 2, (d) 4
mA cm− 2 (e) 10 mA cm− 2, and (f) 20 mA cm− 2 for 1 mAh cm− 2 capacity. Reprinted from Refs. [69] with permission from the American Chemical Society.
6
Journal of Power Sources xxx (xxxx) xxx
solution of zinc sulfate and ammonium sulfate can favor the formation of
hcp basal planes [23]. Similar observations are made for electroplating
solutions containing organic additives polyethylene glycol 8000
(PEG-8000), thiourea, and sodium dodecyl sulfate [62].
2.2.4. Zinc Sponge Electrodes
3D electrode architectures are a growing area of research in the
development of rechargeable zinc batteries and offer a range of advan­
tages such as improved capacity retention, coulombic efficiency, and
reduced dendrite formation. The existence of a continuous conductive
network in 3D electrodes reduces the risk of some zinc particles
becoming electrically isolated and thus electrochemically inactive.
Furthermore, creating an optimized internal porous structure can help
saturate the small volume of electrolyte in the pores and reduce elec­
trode shape change.
There are currently a variety of methods proposed to create 3D zinc
electrodes, which can be grouped into two categories: (i) sponge elec­
trodes that consist almost exclusively of Zn/ZnO [73–76], or (ii) plated
electrodes in which Zn/ZnO is deposited on a separate conductive 3D
substrate such as nickel, copper, or carbon fiber [77,78].
The application of a thermal sintering process is a common method
to create porous 3D structures from zinc metal powder [79]. Recently,
researchers at the United States Naval Research Laboratory have made
significant contributions to the design and manufacturing process of 3D
zinc sponge electrodes [73,75,76,80–82]. In 2014, Parker et al.
described the working concept for zinc sponge electrodes and demon­
strated proof-of-concepts in primary zinc-air and secondary Ag–Zn cells
[73,75]. They did not observe any dendrite formation and attributed the
improved performance to (i) maintaining interconnected metallic
pathways to preserve the long-range electronic conductivity, (ii)
amplifying the electrified interface in 3D such that the current distri­
bution is more uniform, and (iii) restraining shape change in alkaline
electrolytes by sequestering precipitated ZnO within the pores of the
electrode. Recent research has focused on optimizing the manufacturing
process to improve the mechanical stability and volumetric capacity of
the sponges [76]. Alternative green manufacturing methods that bypass
the need to bake the electrodes at high temperatures are also being
investigated [82,83].
N. Borchers et al.
To probe the cycling stability and morphological changes of zinc
sponge electrodes, Bozzini et al. used in situ x-ray computed tomogra­
phy to observe the electrode during electrochemical charge-discharge
cycling [84]. Characterizing the spatiotemporal distribution of Zn and
ZnO in the electrode as well as the degree of connectivity of the
elemental zinc framework, they confirmed that changes in the electrode
structure linked to volume expansion, metal-to-oxide ratio, and conti­
nuity are largely reversible.
2.2.5. Pasted zinc electrodes
Pasted zinc electrodes are porous electrodes which are often used in
commercial cells with alkaline electrolytes. The electrode is manufac­
tured in a discharged state from ZnO and other additives such as bismuth
oxide and calcium hydroxide, for use in an alkaline environment. They
were first used in nickel-zinc batteries [85,86]. The porosity of the
electrode is largely defined during the first charge when the zinc metal
network is created. Pasted zinc electrodes have the advantage of being
simple to manufacture and the additives which control the supply of zinc
to the electrode and the formation of zinc dendrites are positioned
directly in the electrode where they are most needed. Zinc is deposited
inside the electrode, which reduces the risk of forming zinc dendrites
that grow on the outside of the electrode to produce a short-circuit.
2.2.6. 3D printed zinc electrodes
3D printing has recently been reported as an alternative method for
producing porous zinc electrodes [87]. The advantage is that it enables
the design of electrodes with a well-defined microstructure and opti­
mized surface area for maximum zinc utilization. Zhang et al. investigate
3D printed electrodes tested in a zinc-air configuration and report
increased discharge capacity and cycle life and no dendrite formation
[87]. The main challenge related to 3D printing of zinc is the low
melting and boiling temperature at 420 ◦ C and 907 ◦ C, respectively,
which results in massive zinc evaporation if the process is not controlled
properly [88]. The operation window is therefore narrow, and it is
necessary to use an appropriate printing ink. Demir et al. reported that
an ink consisting of relative coarse zinc powder (15 μm diameter) had
better printing properties than using finer zinc powder (9 μm diameter)
[89]. It is also important to keep the oxygen content of the zinc-powder
low. To achieve the right viscosity and share properties Zhang et al.
mixed the zinc powder with carbon black, carbon nanofiber [87]. The
carbon black and carbon nanofibers also improved the mechanical
strength and conductivity of the electrode.
2.3. Benchmarking and standardization
The preceding sections show that there is both great interest in
developing reversible zinc metal electrodes and great diversity in the
proposed approaches. To apply the wealth of materials-level research to
achieve device-level improvements the battery community is pursuing a
set of common standards and benchmarks.
Stock et al. propose a set of seven common descriptors to evaluate
and compare the performance of zinc electrodes in electrically
rechargeable batteries [90]. The seven descriptors are selected to help
enable cross comparison of the practical criteria for reversible zinc
electrodes and focus on: cell properties, utilization, retention, and the
combined performance.
Two ratios are proposed as descriptors for cell performance: the mass
fraction of active material relative to the total mass of the electrode and
the charge capacity of the electrode relative to the volume of the elec­
trolyte. The active mass fraction quantifies the effects of inactive com­
ponents like conducting additives or binder in reducing the specific
capacity of the electrode. It is important to note that the mass of the zinc
electrode changes at different states of charge. The ratio of the active
material capacity to the electrolyte volume is chosen to highlight the
influence of the electrolyte on the observed electrode performance. Lab-
scale batteries are often operated in a surplus of electrolyte, which may
7
Journal of Power Sources xxx (xxxx) xxx
mask some effects of side reaction degradation.
Descriptors describing the utilization of the electrode are the average
specific discharged capacity and the utilization of active material. The
average specific discharged capacity is the quotient of the discharged
capacity and the total mass of the electrode (including additives and
binder). The utilization of active material is the ratio of the amount of
zinc consumed in the discharge to the total amount of zinc present. The
retention of the electrode is quantified by the number of cycles achieved
in the cell and the average coulombic efficiency. The combined perfor­
mance is quantified by the product of the number of cycles and the
average specific discharged capacity.
To create an overview of the state of the art in 2018, Stock et al. [90]
compiled values for the proposed descriptors from 70 papers published
featuring zinc electrodes in alkaline or zinc-air cell configurations. They
note that only a fraction of the papers considered published enough data
to determine the complete set of descriptors. Although values for the
cycle life, average coulombic efficiency, and active material utilization
could be determined from almost all papers considered, the mass frac­
tion of active material in the electrode, the average specific discharged
capacity, and the ratio of capacity to electrolyte volume were under
reported. Fewer than 30% of the papers considered provided informa­
tion on the quantity of electrolyte used in the cell.
The need for standardization applies not only in the reporting of key
descriptors, but also in the testing protocols used to generate them. In a
recent perspective, Ma et al. highlight that although many studies report
outstanding coulombic efficiency values, the same performance has yet
to materialize in real battery cells [70]. They link this discrepancy to the
differences between cyclic voltammetry (CV) and galvanostatic methods
to measure CE. For CV measurements, user-defined potential limits are
often far outside the window of what the zinc electrode would realisti­
cally experience, yielding optimistic CE values. Considering the depen­
dence of the results on user-defined conditions, Ma et al. recommend
using the galvanostatic reservoir half-cell method [70,91–93] to deter­
mine average CE of the electrode. Their work provides a detailed
description of the method combined with suggestions for standard areal
current density, areal capacity, and upper cut-off voltage relevant for
zinc metal electrodes.
There is a wealth of research on the material-level and component-
level performance of zinc-based batteries, but comparatively little
work translating how the observed material behavior would translate to
device-level performance metrics. Parker et al. have provided a helpful
calculation guide to address this gap [4], and Hopkins et al. describe a
specific-energy model to project the system-level characteristics of
rechargeable zinc-air storage [94].
2.4. Outlook
The development of reversible zinc metal electrodes is currently a
topic of intense research and has potential to support the design of high-
energy, safe, and sustainable batteries to supplement lithium-ion bat­
teries. Fundamental understanding of the processes determining the
performance and lifetime of Zn electrodes has rapidly improved over the
past 5 years and led to much progress in the design of zinc-based battery
materials and operating strategies. However, the consolidation of these
research advances into commercially relevant rechargeable electrodes
has lagged. This is due in part to the lack of common standards for
performing experiments (e.g. considering electrolyte volume, coulombic
efficiency characterization method, etc.) and benchmarks for reporting
performance improvements. Recent perspectives from leading groups in
the zinc-based battery community seek to establish and encourage the
use of such guidelines.
Considering the substantial growth in demand for electrochemical
energy storage technology, which is projected to continue to increase for
the foreseeable future, it is necessary to maintain a diverse portfolio of
high-performance battery chemistries. Rechargeable zinc metal elec­
trodes offer a sustainable, safe, high-energy, and low-cost option
N. Borchers et al.
especially for stationary storage applications. The industrial infrastruc­
ture for manufacturing and recycling primary zinc electrodes already
exists, and substantial research progress has been made to address their
limitations as secondary electrodes. Zinc-based batteries will likely
continue to play a role enabling the Green Transition.
3. Zinc-air batteries
Zinc-air batteries (ZABs) combine a metallic zinc anode with an air
cathode to offer an energy-dense, safe, and low-cost energy storage so­
lution. ZABs with alkaline electrolytes are well established as primary
cells and are among the most ubiquitous batteries in use for lightweight
low-power electronics like hearing aids.
The half-cell, precipitation, and full cell reactions for alkaline ZABs
are:
Air Half-Cell 0.5 O2 + H2 O + 2 e− ⇌2 OH−
Zinc Half-Cell Zn + 4 OH− ⇌Zn(OH)2−
4 + 2e
− activity and selectivity comparable to PGMs and excellent cycling
Precipitation Zn(OH)2−
4 ⇌ZnO + H2 O + 2 OH
− stability.
Full Cell Zn + 0.5 O2 ⇌ZnO
When the cell is discharged, oxygen from the air is transported
through the gas diffusion electrode and dissolves into the alkaline
electrolyte, where it is reduced at the catalyst surface to form hydroxide
ions. At the zinc electrode, the zinc metal is oxidized to form zincate, Zn
(OH)2−
4 , which dissolves into the electrolyte. When the concentration of
zincate in the electrolyte surpasses the critical saturation limit, a solid
zinc oxide phase precipitates on or near the zinc electrode. The precip­
itation of ZnO allows the cell to achieve a stable working point and high
energy density but can also lead to the passivation of the electrode at
high current densities.
Zinc-air batteries currently stand alone as the only metal-air battery
chemistry to have been successfully commercialized. However, the
development of rechargeable ZABs has faced hurdles linked to the
reversibility of the zinc electrode, durability of the air electrode, and
degradation of the alkaline electrolyte. Over the last 10 years, these
topics have been the focus of intense research interest with promising
advances. As a result, the first steps towards the commercialization of
rechargeable zinc-air batteries are underway.
The following sections review progress in the development of air
electrode and electrolyte in ZABs, highlighting notable advances from
the scientific literature.
3.1. Air electrode
The air electrode is essential to enable the high energy density values
that make zinc-air batteries attractive. By electrochemically reducing
the oxygen from air, the capacity of the air electrode is unlimited. The
basic design of the air electrode comprises two components: a porous gas
diffusion structure and a catalyst.
Fig. 6. Illustration of the three-phase reaction zone in different electrolytes. Adapted from Ref. [95]. With permissions from WILEY-VCH.
8
Journal of Power Sources xxx (xxxx) xxx
In a primary ZAB, the air electrode must only perform the ORR
during the cell discharge. However, to make the battery rechargeable
the air electrode must be able to also perform the OER. Air electrodes
that are designed to perform both the ORR and the OER are called bi-
functional air electrodes (BAE).
A typical BAE comprises a porous conductive substrate loaded with a
catalyst layer to accelerate the electrode kinetics for ORR and OER as
shown in Fig. 6. The catalyst layer can contain either a single bifunc­
tional catalyst that is active towards both the ORR and OER or a mixed
catalyst system with a different catalyst for each reaction, where the
overpotential of the catalysts towards the ORR and OER and the rate of
diffusion of molecular oxygen to and from the catalytic sites dominates
the specific power and energy efficiency of the battery. BAE design aims
to develop electrodes that are based on a corrosion resistant support and
substrate materials, an optimized porous electrode architecture with
good electronic conductivity, and affordable catalysts with catalytic
Rationally designed BAE with proper porosity, pore structure, elec­
trical conductivity and hydrophobicity is essential to maximize the
macroscopic triple-phase boundary between the catalytic site, electro­
lyte, and molecular oxygen in the electrode structure for the optimal cell
discharge. The porous structure of the BAE should have gas transport
channels, free of electrolyte flooding, to ensure free flow of O2 to the
macroscopic triple-phase boundary during the cell discharge, especially
at higher current densities when the demand for oxygen is high. This is
usually controlled by optimizing the hydrophobicity and porosity of the
electrode structure with the addition of fluoropolymers as binders. On a
microscale, the agglomerates of the catalyst particles are surrounded by
the electrolyte film, where the O2 diffusing in through the hydrophobic
channels gets dissolved. Upon dissolution, the O2 molecules travel
further to the electrocatalytic catalytic sites by diffusing through the
electrolyte film and get reduced [96].
In addition to maximizing the electrocatalyst utilization, the BAE
should be an excellent electrical conductor to facilitate the flow of
electrons to the reaction site from the current collector. Thus, the
addition of fluoropolymers such as PTFE to the BAE structure should be
optimized to not increase the electrode-electrolyte interfacial resistance.
The voltage losses due to the notoriously sluggish kinetics of the ORR
catalyst and the diffusion of molecular oxygen during the discharge
process at high current rates are the most critical in determining the
specific energy of the ZAB. For the OER, a two-phase boundary between
the liquid electrolyte and the solid catalyst is sufficient, provided the
porous electrode structure transports the evolved oxygen efficiently
from the reaction site to avoid the loss in the active surface area to the
gas bubbles.
Fig. 7 shows the typical charge/discharge behavior of a ZAB, where
the half-cell performance of the zinc electrode and the BAE is plotted for
increasing current densities. It is observed that the cell voltage of the
ZAB closely follows the BAE potential, signifying the importance of the
N. Borchers et al.
Fig. 7. Charge/discharge profile of a ZAB cycled at different current densities.
Both the half-cell potential of the individual electrodes and the full cell voltage
are displayed. Zinc electrode, 25 cm2 area: Zn paste (Zn + ZnO) with Cu mesh
current collector; Electrolyte (static, 4 ml): 7 M KOH; separator: glass fiber, 2
numbers, 900 μm total thickness; BAE: NiCO2O4 + Ni powder + PTFE +
stainless steel current collector.
overpotential losses at the BAE to the energy efficiency of the ZAB.
3.1.1. Challenges
The performance and cycle life of the air electrode is affected by the
degradation of the catalysts and catalyst layer as well as the gas diffusion
structure. The loss of electrocatalytic activity, dissolution of catalysts,
and shedding of catalysts occurs during the ZAB operation, especially
due to exposure to high voltages during charging and repeated charge/
discharge cycles. The loss of active materials, which is accelerated at
high charging current densities due to the enhanced production of O2,
would lead to the reduction in electrochemical surface area (ECSA) thus
affecting the specific energy of the ZAB. The porous structure of the BAE
will inevitably be infiltrated and flooded with the electrolyte during the
ZAB operation due to the volume change inside the cell including the
zinc electrode. Operating the ZAB at higher current densities would
accelerate the BAE flooding due to larger volume change of the zinc
anode. In addition, atmospheric humidity would also cause flooding or
drying out of the BAE, if not properly managed [97]. Another failure
mode of the BAE is the obstruction of pores due to the precipitation of
carbonates after saturation, which are formed through the reaction of
the alkaline electrolyte with CO2 from the atmosphere [98].
3.1.1.1. Catalyst activity, stability, and selectivity. Air electrode catalysts
must possess a delicate combination of characteristics to be successful. A
good catalyst should be active towards the ORR, the OER, or both. It
must be stable in the electrochemical environment of the electrode over
a wide potential range covering the charge and discharge voltage regime
of the ZAB. Particularly, the ORR catalyst should favor the complete
reduction of oxygen through a direct 4e- pathway, instead of a 2e-
pathway of oxygen reduction to hydrogen peroxide [99].
The kinetics, stability, and affordability of catalysts for the ORR and
OER are among the most important factors for the success of the elec­
trically rechargeable ZAB technology. Pt-group metal (PGM) catalysts
such as Pt and Pt alloys for the ORR and IrO2, and RuO2 for OER are the
most active electrocatalysts with reasonably low overpotentials in the
alkaline media [100,101]. However, PGM-based catalysts are expensive
because of their limited availability, and their long-term cycling stability
is still questioned considering the potential dependent corrosion and
dissolution of Pt at water oxidation potentials, as well as catalyzing the
corrosion of the carbon support [102]. Besides, the advancement of
ZABs as a low cost and sustainable alternate battery technology for
9
Journal of Power Sources xxx (xxxx) xxx
energy storage does not justify the use of PGMs.
3.1.1.2. Carbon corrosion. The practice of using carbon-based sub­
strates and support materials for their excellent electrical conductivity,
and to enhance the electrochemical active surface area (ECSA) of the
catalysts shortens the lifetime of the conventional bifunctional air
electrode (BAE) due to the corrosion of carbon at high potentials during
charging. The oxidation of carbon would lead to the loss of catalyst
ECSA, alteration of pore morphology, loss of interparticle contact and
active material shedding. Although highly graphitized carbon particles
are found to show enhanced corrosion resistance, they are still not
suitable for high current operations of ZABs [103]. Recently, Xu et al.
reported the cycling stability of BAEs comprising a binder-free MnO2
coated Ni foam as the support substrate together with a gas diffusion
layer (GDL) consisting of carbon nanotubes (CNT) and PTFE [104]. The
hydrophobized GDL was employed to improve the water management
for the BAE during cycling. The authors observed significant degrada­
tion of the GDL, especially at a high current density of 50 mA cm− 2. The
internal structure of the GDL was destroyed due to carbon corrosion,
which critically limits the electron and mass transfer pathways con­
structed by the CNT network. Although, the deactivation of the MnO2
catalyst contributed to the performance loss during cycling, the
destruction of the carbon-based GDL was highlighted to be the main
reason for the cell failure.
3.1.2. Progress
3.1.2.1. Catalysts. Among the various non-PGM catalyst materials
being developed for ZABs, transition metal oxides (TMO), carbon-based
materials and metal organic frameworks (MOF) are the three most
promising categories. The following section summarizes the recent de­
velopments in the bifunctional catalysts for ZABs within these major
categories. More extensive discussions on the development of ORR,
OER, and bifunctional catalysts for ZABs are extensively reviewed in
these papers [105–109].
TMOs are among the most preferred bifunctional catalysts due to
their high activity for the ORR and OER and low cost. Other major ad­
vantages of transition metal oxides include affordability, ability to use
non-toxic, more abundant, sustainable, and environmentally friendly
elements [110–112]. TMOs include a range of single metal oxides, spi­
nels (AB2X4, A, B = metal, X = chalcogen), or perovskites (ABO3, A, B =
metal).
Oxides of manganese, which is one of the most abundant and non-
toxic elements, exist in more than 20 different polymorphs. Manga­
nese oxide polymorphs are non-stoichiometric and multivalent. The use
of MnOx materials in batteries is not new. MnOx with different structural
forms are being used as the active cathode material in primary zinc-air,
zinc-carbon, and alkaline-MnO2 batteries for many years. As an oxygen
reduction catalyst, the polymorph α-MnO2, with good electronic con­
ductivity and a distinctively larger tunnel size, is found to be intrinsi­
cally more active for the ORR. The order of ORR and OER activity for the
different polymorphs is found to be: δ-MnO2 < β-MnO2 < α-MnO2.
Comparing the performance of the catalyst vs. base metal cost, α-MnO2
is found to outperform Pt/C significantly on the ground of catalytic
activity per material cost [99,113].
TMOs based on spinels and perovskites offer several possibilities to
tune the catalytic activity. The most adapted strategies to promote the
bifunctional activity of spinels (Co3O4, NiCo2O4, NiFe2O4, CoFe2O4,
MnFe2O4, etc.) and perovskites (LaCoO3, LaNiO3, LaMnO3, etc.) are
through controlling the phase and composition, valence state control by
cation doping, create oxygen vacancies by engineering defects to modify
the electronic structure, tailoring of morphology and microstructure
[110–112,114–118]. Engineering the morphology and microstructure of
the oxides is especially critical on the electrode level as they determine
the surface area, and mass transport networks within the aggregate.
N. Borchers et al.
Conventional high temperature synthesis methods like solid-state
and sol-gel method that produce agglomerates with low surface area
and electronic conductivity. A wide range of contemporary methods
such as template-assisted method, flame spray pyrolysis, electro­
spinning, and the hydrothermal method are explored [108,119] to
produce catalysts with unique three-dimensional and one-dimensional
microstructures containing tailored mesopores and macropores. These
characteristics are considered to increase the ECSA, electronic conduc­
tivity, and facilitate mass transport networks for oxygen and hydroxyl
diffusion [120,121]. Besides oxides, other forms of 3d-transition metals
such as alloys, metal hydroxides, carbides, dichalcogenides, nitrides,
phosphides, and selenides with regulated crystal and electronic struc­
tures are also reported to show good bifunctional activity in the alkaline
media [122–126].
The corrosion of carbon is thermodynamically favored to occur at air
electrode potentials. Nonetheless, different carbon-based materials are
investigated as bifunctional catalysts for the ZABs owing to their
excellent electronic conductivity, higher degree of graphitization, and
the possibility to the tailor the catalytic activity by tailoring the elec­
tronic structures through heteroatom doping and surface functionali­
zation. Doping carbon structures such as nanotubes [127,128],
nanosheets [129,130], nanocages [131], nanoribbons [132], nano­
spheres [133], foams [134,135], 2D graphitic sheets [125,136] with a
single or multiple heteroatom (B, N, O, P, S) is one of the most effective
strategies to improve the bifunctional activity, as the doping is consid­
ered to modify the charge density distribution of the adjacent carbon
atoms. It has been demonstrated that in N-doped 3D-graphene nano­
ribbons, the availability of electron-withdrawing pyridinic N moieties in
the structure promotes OER, while the electron-donating quaternary N
sites catalyze the ORR [132]. Composites of carbon structures with
metals, metal oxides, and metal hydroxides were also investigated
extensively for their electrocatalytic activity [99,137]. Even though a
vast number of research activities show promising bifunctional activity
for the carbon-based structures, the origin of catalytic activity is still
disputed due to lack of fundamental understanding of the complex
catalytic surface containing vacancies, crystalline disorder, dangling
groups, etc. [127,131,138].
Bifunctional catalysts derived from metal organic frameworks (MOF)
are one of the most recent advances in electrically rechargeable ZABs.
The ordered porous framework of MOFs offers unique advantages such
as high surface area for the active sites and an interconnected pore
network for enhanced charge transfer and mass transport in the cata­
lysts. Many different types of catalysts such as metals, metal oxides, etc.,
and multiple catalyst mixtures could be obtained within the MOF
framework to tailor the electrocatalytic bifunctional activity. Some of
the challenges currently faced by MOF-based catalysts are low electronic
conductivity and stability of the pristine MOFs, which are generally
mitigated by thermal treatments. However, the ordered porous frame­
work of the MOFs is destroyed with high temperature annealing.
Although the laboratory-scale performance of the MOF-derived bifunc­
tional catalysts are promising, challenges concerning high-volume pro­
duction, reproducibility, cost, cumbersome post-synthesis MOF
modification steps, and lack of fundamental understanding on the con­
version of MOFs and their decomposition during thermal treatments
must be addressed [107].
3.1.2.2. Substrates and gas diffusion structures. The development of non-
carbon substrate materials to avoid the deleterious effects of carbon
corrosion on the air electrode stability is an on-going topic. Current
research on BAEs focuses on using Ni foam or stainless-steel mesh as the
electrode substrate [139–141]. Ni foams are of particular interest, as
they offer a three-dimensional architecture that would increase the
structural integrity, electronic conductive network, porosity, and
improved catalyst utilization. When exposed to higher potentials in the
alkaline medium, Ni oxidizes to form a passivating film that protects the
10
Journal of Power Sources xxx (xxxx) xxx
metal from further oxidation, thus offering better corrosion resistance
than carbon [141]. When suspended in an alkaline medium Ni metal
readily forms Ni(OH)2. During the charging process, Ni(OH)2 oxidizes to
Ni(OOH). The process is reversible, i.e. during discharge, Ni(OOH) re­
duces to Ni(OH)2.
Recently, porous Ni foams are preferred as the conductive substrate
for the development of binder-free BAEs. Various design strategies with
the objectives of lost-cost fabrication method, cycling stability and high
energy efficiency have been proposed. Wan et al. reported a Janus-type
integrated BAE with individual catalysts for the ORR and OER. The
authors used electrodeposition to coat MnOx for ORR and FeNi for OER
on either side of the Ni foam to develop binder-free BAEs, where the
ORR catalyst was exposed to the air side and the OER catalyst is exposed
to 6 M KOH. The BAE demonstrated stable performance for more than
100 hours with 5% loss in the cycling efficiency at 10 mA cm− 2 [142].
Chen et al. grew nanolayers of N-doped NiFe double layered hydroxide
were grown directly on a nickel foam to create a binder-free poly­
crystalline layered structure through the chemical bath deposition
method. The BAE showed excellent mechanical flexibility, large mac­
ropores with a high catalyst utilization [140]. Nevertheless, the
long-term stability of nickel-based during the ZAB operation is still
questionable.
Cano et al. carried out a detailed research on the durability of Ni-
based BAEs by investigating the effect of nickel (oxy)hydroxide passiv­
ating film on the catalyst performance [96]. The BAE was fabricated
conventionally with PTFE as binder, Ni powder as the conductive sup­
port and NiCo2O4 as the bifunctional catalyst. The surface morphology
of the BAE was investigated before and after 100 cycles in a ZAB
configuration. The flakes of NiCo2O4 catalysts that were observed before
cycling were not visible after cycling. A spongy film, which was inves­
tigated to contain both Ni(OOH) and Ni(OH)2 had grown around the
catalyst particles during cycling. The presence of Ni(OH)2 on the elec­
trode surface at the charged state revealed that the Ni(OOH) was not
completely reduced during discharge. The authors found that the com­
bination of activation and mass transport losses due to the growth of Ni
(OOH) film over the catalyst particles led to an increase in the ORR
overpotential over ZAB cycling.
3.1.2.3. Three electrode configuration. The three-electrode configuration
features two positive electrodes: one used for the ORR when the cell is
discharged, and one used for the OER when the cell is charged. Using
different positive electrodes for the charging and discharging process
gives designers more flexibility to select appropriate catalysts for the
ORR and OER, implement simpler electrode architecture exclusively
designed for the charge and discharge process, and achieve high cycle
life through limited catalyst and electrode degradation. Additionally,
carbon-based materials that are highly conductive and affordable can be
used in the ORR electrode without any concerns on corrosion.
The choice of catalysts and substrates for the OER electrode is vast as
it benefits from the wide range of research on water oxidation anodes for
alkaline electrolyzers. A carbon-based gas diffusion electrode (GDE)
with Ag or MnOx catalyst and porous sintered nickel structure or
stainless-steel grid are the materials of choice for the ORR and OER
electrode. Nevertheless, the practical relevance of the three-electrode
configuration is limited by the additional weight and volume as well
as the complexity in the cell design and battery management system
added by the additional electrode, resulting in lower specific power and
higher cost per kWh [143,144].
3.3.1. Benchmarking and standardization
Over the last decade, the development and optimization of air elec­
trode catalysts, substrates, and designs has spawned hundreds of
research papers. Despite this intense research interest, the development
of competitive bi-functional air electrodes has made slow progress. One
challenge hindering development is the lack of standardization for the
N. Borchers et al.
conditions used to measure and benchmark air electrode performance.
The most acceptable way of benchmarking the bifunctional catalysts
is to determine the potential difference (ΔE) between the OER (charge)
potential at 10 mA cm− 2 (E10) and the ORR (discharge) potential at the
half-wave potential (E1/2, the potential at half way to the limiting cur­
rent density) through rotating disk electrode (RDE) measurements
[145]. The catalysts with smaller ΔEs are preferred as they offer lower
overpotentials for the ORR and OER. At the full cell level, measuring the
energy efficiency between the charge and discharge process by dividing
the charge voltage by the discharge voltage at a particular current
density is the most common descriptor to evaluate the cell performance.
Due to the high overpotentials of the BAE, an energy efficiency for the
ZAB is typically limited to <60–70% [146,147].
The need for air-electrode standardization was recently discussed by
Hopkins et al. [148], who advocate for a standard discharge energy of
35 mWh cm-geom2. This value is derived from an analytical model to
represent a zinc-air battery that is comparable to the specific energy of a
lithium-ion pack-level specific energy of 120 Wh kg-pack1. In their anal­
ysis, Hopkins et al. considered published studies of 100 zinc-air batteries
and note that the reported areal energy values span five orders of
magnitude. The vast difference in the reported electrode cycling con­
ditions makes a reasonable cross comparison of the results very difficult.
Only 8 of the 100 studies considered exceeded the 35 mWh cm-geom2
threshold.
3.4.1. Outlook
An abundance of research has been carried out on the development
of non-PGM catalysts and targeting high performance BAEs for
rechargeable ZABs. Nevertheless, as with fuel cells, translating the high
electrocatalytic activity of catalysts achieved through rotating disk
electrode (RDE) measurements to practical electrodes remains
challenging.
It is essential to develop low cost and environmentally friendly high-
volume production processes for the novel electrocatalysts without
sacrificing their advantages on their physicochemical properties. On the
BAE front, other than a few, systematic studies on long-term stability of
the BAEs under actual ZAB operating conditions are sparse. The cycling
stability of many conductive support materials and substrates being used
in the ZAB are questionable. Much of the knowledge on BAE develop­
ment is grounded in progress from alkaline fuel cells and electrolyzers
technology, where the materials do not undergo shifts between
oxidizing and reducing conditions as with the ZAB.
New model-based design processes and manufacturing methods for
engineering optimized electrode structures with high-performance cat­
alysts, utilization, and structural stability is essential for further devel­
opment. Newer approaches, including the integration of anion-
conducting solid polymer membrane on to the BAE to prevent the ZAB
from degradation from external elements such as humidity and CO2
should be considered.
3.2. Electrolyte
The electrolyte is responsible for the transport of charge-carrying
ions in the cell and supporting the electrochemical reactions at the
electrode-electrolyte interfaces. The electrolyte should have a high ionic
conductivity, low electrical conductivity, and be stable in the electro­
chemical window of the cell. In open systems like zinc-air batteries, the
electrolyte should also be stable in air, have a low vapor pressure, and
avoid toxic materials.
Aqueous electrolytes have the advantage of being low-cost and non-
flammable. Solutions of strong bases like KOH are especially advanta­
geous due to their high ionic conductivity. For these reasons, concen­
trated solutions of KOH have been the industry standard for aqueous
zinc batteries for more than 50 years.
Traditionally, the design of alkaline electrolytes has focused on
optimizing a few critical parameters like ionic conductivity, zinc and
11
Journal of Power Sources xxx (xxxx) xxx
oxygen solubility, and viscosity as a function of the KOH concentration.
A short comparison of these properties shows that the peak ionic con­
ductivity occurs for concentrations between 5 and 7 M at 298 K [149].
As a result, concentrated KOH electrolytes saturated with Zn(OH)2- 4 are
common baseline electrolyte for alkaline batteries. In many ways, this
approach is effective for designing electrolytes for primary zinc systems.
However, the need for long-life rechargeable batteries brings new
challenges which requires a more nuanced approach to electrolyte
design.
3.2.1. Challenges
3.2.1.1. Carbonation. In zinc-air batteries, the electrolyte is exposed to
air containing approximately 400 ppm of CO2, which can dissolve in the
electrolyte. In alkaline media, dissolved CO2 reacts with hydroxide to
form carbonate ions.
CO2 + 2 OH− ⇌CO2−3 + H2 O (6)
Carbonate is a salt of carbonic acid, which exists in various proton­
ated states depending on the pH. H2CO3 is dominant below pH 6, HCO−3
is dominant between circa pH 6–10, and CO2− 3 is dominant above pH 10.
H+ + CO2−3 ⇌HCO−3 , pKa = 10.00 (7)
H+ + HCO−3 ⇌H2 CO3 , pKa = 6.16 (8)
The formation of carbonates presents a variety of challenges for the
battery. The conversion of highly mobile OH- ions to CO2− 3 lowers the
ionic conductivity of the solution, lowers the concentration of OH- and
slows the kinetics of the ORR. Furthermore, zinc carbonates have a very
low solubility and can precipitate in both electrodes.
Although the carbonation of the electrolyte can be slowed by
applying CO2 filters to scrub the air feed, this adds cost and complexity
to the system. Furthermore, to reach practical battery lifetime, the
concentration of CO2 in the feed gas would need to be reduced by two
orders of magnitude [41]. Other approaches to deal with this challenge
include: (i) the use of near-neutral electrolytes or (ii) solid-state
electrolytes.
3.2.2. Progress
3.2.2.1. Near-neutral electrolytes. Recent interest in rechargeable zinc-
air batteries has renewed investigations into different aqueous electro­
lyte compositions with near-neutral pH values that can minimize per­
formance degradation due to CO2 dissolution and improve the
homogeneity of zinc deposition.
Near-neutral solutions of NH4Cl and ZnCl2 were some of the first
electrolytes to be used in zinc-based Leclanché cells and were briefly
revisited in the late 20th century for zinc-air batteries [150]. In
near-neutral zinc-air cells, the ORR and OER alter the local concentra­
tion of H+ in the air electrode. NH+4 acts as a pH buffer to stabilize these
concentration shifts, and the resulting NH3 forms complexes with Zn2+
ions in the solution.
0.5 O2 + 2 H+ + 2 e− ⇌H2 O (9)
NH+
4 ⇌NH3 + H
+
(10)
Zn2+ + x NH3 ⇌Zn(NH3 )2+
x (11)
The concept was revived in the early 2000’s to pursue commercial
grid-scale rechargeable ZAB systems with improved resilience towards
CO2 dissolution [151,152]. Research has shown that such near-neutral
electrolytes can indeed extend the lifetime of rechargeable ZABs in air
[153,154], but they also bring new challenges.
To maintain a stable pH, a buffering species must continuously be
supplied to the cathode. To stabilize the pH during the OER, there must
N. Borchers et al.
be NH3 present to accept H+ created in the reaction. However, the
equilibrium concentration of NH3 in the near-neutral pH domain is low,
and concentration gradients that develop during normal operation can
lead to the local depletion of NH3 species in the air electrode. In 2017,
Clark et al. developed a continuum modelling framework capable of
efficiently simulating the intricate interactions among Zn2+ and pH
buffering species in zinc-air cells [155]. They predicted that the pH in
the air electrode can become strongly acidic during charging and
exacerbate the degradation of the catalyst through metal dissolution.
This prediction was experimentally confirmed in near-neutral zinc-air
batteries [156] and analogous observations have since been made in
zinc-ion cells [157,158].
Many transition metal catalysts are stable under alkaline and near-
neutral conditions but are more soluble in acidic media. This can lead
to the loss of active surface area and degradation in cell performance
over time. In addition to effectively stabilizing the pH with a buffer
solution, some research proposes dissolving metal salts into the elec­
trolyte to help suppress the driving force for catalyst dissolution.
The precipitation of non-ZnO phases as the solid discharge product is
an additional challenge for zinc-air batteries with near-neutral electro­
lytes. In a zinc-air battery, the precipitation of ZnO is needed for the cell
to achieve a stable working point and achieve a high energy density.
However, mixed zinc salts are often less soluble in near-neutral solutions
than ZnO. As a result, solids containing electrolyte species can precipi­
tate during the discharge process of the cell. In Leclanché electrolytes,
Clark et al. predicted that the initial precipitation of a chloride-rich
phase would deplete the local concentration of chlorides in the elec­
trolyte eventually inducing a shift towards hydroxide-rich phases. This
prediction was confirmed experimentally [156]. An analogous challenge
is reported in zinc-ion batteries in which the parasitic precipitation of
zinc sulfate hydroxide phases can have similar effects.
Recent developments in near-neutral electrolyte design seek to
identify compositions that maintain stable pH values throughout cycling
and favor the precipitation of ZnO as the final discharge product. Clark
et al. identified a combination of carboxylic and amino acids that ach­
ieve the desired behavior, but undergo side-reaction degradation during
electrical recharging [159]. Dilute solutions of NaCl and seawater have
also been proposed for low-cost zinc-air batteries [37,160].
3.2.2.3. Solid-state electrolytes. Solid-state electrolytes including anion-
exchange membranes (AEM) and alkaline gel electrolytes (AGE) have
the dual benefits of improving the resilience of the electrolyte against
carbonation and enabling the development of flexible zinc-air cells.
Flexible metal-air batteries and their associated electrolytes are a
growing area of interest and the subject of dedicated reviews [161–163].
AGE membranes are generally fabricated by mixing an alkaline salt
(e.g. KOH) and a host polymer in an aqueous solution followed by
resting at a low temperature to form a solid-state gel electrolyte. Com­
mon host materials include poly (vinyl alcohol) (PVA), polyacrylic acid
(PAA), polyethylene oxide (PEO), N-vinyl-2-pyrrolidone, vinyl imid­
azole, and glycindyl methacrylate. The obtained ionic conductivity of
the AGE membranes varies according to the host material and concen­
tration of dissolved KOH. Xu et al. used a mixed host of PVA and PEO
with 8.3 wt% KOH to create a highly flexible membrane with an ionic
conductivity of 0.3 S cm− 1, which is close to the ionic conductivity of
KOH solution at the same concentration [164]. Additionally, PAA with
36 wt% KOH has demonstrated ionic conductivity up to 0.46 S cm− 1
[165].
In aqueous electrolytes, the porous electrode surfaces are sufficiently
wetted by the non-viscous liquid. However, achieving proper electrode
wetting is a challenge for solid-state electrolytes, as shown in Fig. 6. Poor
wetting can lead to high interfacial resistance, particularly at the
catalyst-electrolyte interface. Micro-porous solid electrolytes with high
hydroxide ion capacity and selectivity are needed.
Bertolotti et al. proposed that synthesizing a PECH network directly
12
Journal of Power Sources xxx (xxxx) xxx
on the electrode improved the surface coverage in the porous structure
and led to an improved membrane-electrode interface [166]. An elec­
trode protected with a PECH/Fluorolink MD700 interpenetrating poly­
mer network (IPN) in an alkaline Li-air configuration demonstrated an
increase in air electrode stability up to 1000 hours, a 20-fold improve­
ment over a non-protected electrode [167].
4. Zinc flow batteries
Flow batteries can be divided into two categories: (i) those in which
the energy or active material is stored outside the electrochemical
converter or “battery” (see Fig. 2c) and (ii) those in which the part or all
the active material is stored inside the battery (see Fig. 2d), they are
sometimes called “hybrid flow batteries” [168]. In the first type of flow
battery, the energy stored will depend on the size of the container for the
active material and the discharge time can in theory be infinite. In the
second type of flow battery, the amount of energy it can store will
depend on the amount of active material, in this case zinc, that can be
stored inside the battery.
The first type of zinc flow batteries are mostly zinc-air batteries that
use flowing zinc paste or zinc pellets as the active material, which is
stored and regenerated outside of the battery. During discharge, the
negative electrode is fed with the metallic zinc and the discharge
products (ZnO and zincate solution) is regenerated in a separate reactor
[169]. These can be considered as primary or “mechanically recharge­
able” batteries, since the battery only undergoes electrical discharging.
In the second type of zinc flow battery, zinc metal is plated on the
negative electrode on charge. The favorable electronic conductivity of
zinc together with a very good interface means they have better power
densities compared to other flow batteries. However, they are limited in
energy, typically 4h of discharge, by the thickness of zinc that can be
plated onto the negative electrode without forming dendrites and short-
circuits with the positive current electrode. One of the main challenges is
to increase this storage beyond 4h in order to decrease the kWh cost.
The most common and more mature technology is the zinc-bromine
flow battery which uses bromine, complexed bromine, or HBr3 as the
catholyte active material. The bromine couple has the advantage of fast
kinetics (high power) and the bromine and complexed bromine (with
organic amines) formed forms a separate immiscible liquid phase which
sinks. This enables membrane-less flow batteries to be conceived and
zinc flow batteries without a separating membrane are now commercial
[32]. The ion-exchange membrane in flow-batteries is one of the biggest
if not the biggest cost contribution of the battery. Other less developed
catholytes for zinc flow batteries include ferricyanide, redox active
soluble organic compounds [170] such as quinones and TEMPO, and
polymer suspensions such as polyaniline [171], cerium sulfate, iodine,
or even chlorine [172].
5. Nickel–zinc batteries
Nickel-zinc batteries make use of alkaline electrolytes and rely on
hydroxide as main charge carrier. Thus, they offer high power-densities
and long cycle life. Research on nickel-zinc batteries has paused due to
low practical capacities. However, recent research motivated by the ban
of nickel-cadmium batteries in the European Union lead to remarkably
progress and might revive the research. Cobalt-free nickel electrodes
were produced with competitive energy densities of 165 Wh kg− 1 for a
small pouch cell at low cost [173].
6. Zinc-ion batteries
Zinc-Ion batteries recently attracted a lot of interest and showed
great innovation. Although zinc-ion batteries use similar electrode ma­
terials as primary alkaline Zn–MnO2 batteries, they make use of different
electrolyte materials to shuttle zinc ions as the main charge carrier in the
battery. The use of a zinc-ion shuttle mechanism makes them unique
N. Borchers et al. Journal of Power Sources xxx (xxxx) xxx

among the zinc-based battery cells and resembles the shuttle mechanism
in modern lithium-based batteries. The shuttle mechanism is a key
design feature improving rechargeability in modern zinc batteries.
Batteries using this charge/discharge mechanism are called “zinc-ion
batteries” in almost all recent publications [7,174]. However, their use
of a zinc metal electrode more closely resembles lithium metal batteries.
Thus, the terms zinc metal or zinc shuttle batteries would technically be
more appropriate.
Primary alkaline zinc batteries with manganese dioxide cathodes
commercialized in the 1960s were a significant step forward in con­
sumer batteries. Because of their cost and robustness, they dominated
the consumer battery market [175,176]. This improvement in battery
technology drove many portable electronics developments. Primary
alkaline zinc batteries still play an essential role in today’s battery
landscape. Nevertheless, both the increased energy requirements of
mobile devices and the demands in electromobility have led to a decline
in research interest in favor of lightweight rechargeable cells like
lithium-ion batteries.
These cells, also known as alkaline batteries, feature a zinc powder
anode and a cathode composed of electrodeposited MnO2 as active
material within a concentrated KOH solution. During discharge, the
anodic zinc is oxidized and forms zincate ions (Zn(OH)2- 4 ) in alkaline
electrolytes. The negatively charged zincate accumulates at the anode
during the discharge and precipitates as ZnO releasing hydronium ions.
At the cathode, protons are intercalated into MnO2 to form MnOOH. OH-
ions mediate the charge between the half-cells. While the single electron
reaction gives a theoretical capacity of around 300 mAh g-1 and is
recognized as a reversible process, a second electron reaction via a
dissolution-precipitation mechanism irreversibly reduces MnOOH to Mn
(OH)2 [177]. Additionally, the conversion of MnO2 to MnOOH decreases
the cathode’s electric conductivity, leading to poor performance at high
rates.
The modern rechargeable version of these high energy zinc batteries
relies on mildly acidic electrolytes (see Fig. 2b). Despite the apparent
similarity to alkaline batteries, they feature a distinctly different cell
reaction. Zinc does not stay in the anode and does not precipitate as zinc
oxide. This mitigates the risk of anodic passivation by ZnO precipitates.
Instead, zinc is used as a charge carrier and intercalates into the cathode
active material, e.g.,
Zn2+ + 2 MnO2 + 2 e− →ZnMn2 O4
6.1. Challenges
The development of zinc-ion batteries is a comparatively new field.
Nazar and co-workers [178] highlight that the “infancy” of zinc-ion
battery research leads to unclear cathode design goals. Moreover,
Table 1
Selection of proposed insertion/conversion reactions of cathode materials in
zinc ion batteries and their theoretical gravimetric energy densities. The amount
of zinc per unit-cell is selected according to the reported amounts in literature.
Material Proposed reaction Specific capacity
MnO2 Zn2+ + 2 MnO2 + 2 e− ⇌ ZnMn2 O4 1
308,3 mAh⋅g−MnO
2
different reaction mechanisms are observed for the same cathode ma­
terial in the literature. A selection of the reaction mechanisms discussed
in literature is shown in Table 1. Exemplary, for MnO2 cathodes it is
unclear whether the cathodic capacity is derived solely from the inter­
calated zinc, or strongly affected by the intercalation of H+ combined
with the reversible precipitation of zinc salts. Even the dissolution of
Mn2+ is discussed as desired reaction mechanism. The intercalation
chemistry at the cathode and reactions at the electrode-electrolyte
interface are relatively unknown. Thus, the elucidation of the cathode
reaction mechanism and the search for a viable combination of cathode
materials and electrolyte salts dominates the current research.
6.2. Progress
The main objective for the cathode design is the reversible interca­
lation of the charge carrier into the host structure. For zinc ions, the host
structure must be a material with vacancy sites and stable structures that
remain intact upon the intercalation of divalent ions. The layered, tun­
nel, or spinel structures found in metal oxides are most common. Several
materials have successfully demonstrated intercalation of zinc. Among
them, manganese and vanadium oxides currently receive most interest.
Prussian blue analogs and organic quinones also show some interesting
properties and might experience increasing interest for specialized ap­
plications. An overview over these cathode active materials and typical
energy vs. power densities is given in Fig. 8.
Both vanadium and manganese oxides are polymorphic with many
oxidation states for the metal ions. A broad range of crystallographic
configurations offer host sites for zinc atoms. However, these materials
often suffer from capacity losses due to the dissolution of the host metal
in the mildly acidic electrolyte. Phase transformations induce mechan­
ical stress, limit solid-state diffusion of zinc, and alter electrolyte pH
through release or insertion of H+. Nevertheless, the polymorphs of
manganese dioxide are the most researched material for zinc shuttle
batteries as they offer a good compromise between cycling stability and
capacity.
6.2.1. Manganese dioxides
Electrodeposited manganese dioxide cathodes were successfully
recharged in near-neutral electrolytes in the 1980s [179,180]. Limited
cyclability and phase change after several cycles caused research to
(12)
stagnate. Nevertheless, in 2012 the usage of α-MnO2 [181] revived
research interest as it showed better reversibility and high coulombic
efficiency at deep discharge and led to a rapid growth in publications on
the topic.
α-MnO2 is a polymorph with 2x2 tunnels, shown to intercalate many
multivalent ions [182,183]. As demonstrated by Kang et al. [181], zinc
insertion during cell discharge changes the oxidation state from Mn(IV)
to Mn(III) and forms ZnMn2O4. Subsequently, several polymorphs were
tested successfully. Various reviews provide a detailed overview of their
respective working principles [7,178,184,185].
The early study of Kang et al. is particularly informative as different
MnO2 polymorphs are compared in a ZnSO4 electrolyte [186]. Layered
δ-MnO2 has the highest specific capacity of 269 mAh g− 1. The
tunnel-like polymorph yields a capacity of 234 mAh g− 1 (α-MnO2), the
1x1 structure gives 213 mAh g− 1 (β-MnO2) and the 1x2/1x1 structure

H+ + MnO2 + e− ⇌ MnOOH 1
308,3 mAh⋅g−MnO
gives 201 mAh g− 1 (γ-MnO2). These were quite reasonable capacities
2

2 H+ + MnO2 + 2 e− ⇌Mn(OH)2 1
616,6 mAh⋅g−MnO2
compared to the theoretical capacity of 308 mAh g− 1 for reduction from
Mn 2+
+ 2 H2 O⇌MnO2 + 4 H + 2 e
+ − 616,6 mAh⋅g−MnO
1
2
Mn(IV) to Mn(III).
V2O5 Zn2+ + V2 O5 + 2 e− ⇌ZnV2 O5 294,7 mAh⋅g−V21O5
Although zinc intercalation [187] is the mainly reported charge
V3O7⋅ H2O 2 Zn2+ + V3 O7 ⋅H2 O + 4 e− ⇌Zn2 V3 O7 ⋅ 379,0 mAh⋅
storage mechanism [7,174], there is an ongoing debate about the
H2 O g−V31O7 ⋅H2 O
contribution of other processes. Sun et al. report the co-intercalation of
VS2 Zn 2+
+ 2 VS2 + 2 e ⇌ZnV2 S4 232,7 mAh⋅g−VS12
Zn2+ and H+ in a MnO2 cathode electrodeposited on carbon fiber paper
−

CuHCF Zn2+ + 2 CuFe(CN)6 + 2 e− ⇌ 1

85,2 mAh⋅g−CuHCF in a 2 M ZnSO4 + 0.2 M MnSO4 electrolyte. Ex-situ XRD measurements
( )
Zn CuFe(CN)6 2 during discharge indicate a two-phase mechanism, zinc is inserted first
Calix [4] 4 Zn2+ + C4Q + 8 e− ⇌Zn4 C4Q 1
446,3 mAh⋅g−C4Q before protons are inserted at voltages above 1.3 V. This is validated by
quinone
discharge in pure 0.2 M MnSO4 electrolyte without zinc, which does not

13
N. Borchers et al.
Fig. 8. Overview of the reported properties for cathode materials in aqueous zinc-ion batteries. The average operating voltage is estimated from the observed voltage
window during discharge. Both manganese oxides as well as vanadium compounds reach cathodic energy density above 400 Wh•kg− 1. The insets show represen­
tative crystal structures as examples of the respective material class. The underlying datapoints on operating voltage and capacity were extracted from.
show distinct plateaus and only achieves the capacity of the proton
insertion process. Pan et al. [188] investigated α-MnO2 – nanorods as
well in a 2 M ZnSO4 + 0.2 M MnSO4 electrolyte and similarly concluded
that the cathode undergoes a conversion reaction with H+ and forms
MnOOH. This induces a chain of side effects: the pH increases and zinc
precipitates as ZnSO45[Zn(OH)2]3•xH2O in the cathode. Such a precip­
itation of hydroxide sulfates is unfavorable because it endangers the zinc
transport and alters the electrolyte composition.
Phase transformations of manganese oxide are frequently observed
during cycling. In most cases, manganese oxide transforms into the
layered zinc-buserite form during zinc insertion and releases Mn2+ into
the electrolyte. Lee et al. [189] proved that this phase transformation is
in principle reversible and it is shown that addition of Mn2+ to the
electrolyte successfully increases the reversibility of transformation
between α-MnO2 and the layered buserite [188,190]. Recent studies
propose to make use of this reversible deposition and dissolution of
Mn2+ [191,192]. During discharge, electrolytic Mn2+ is deposited as
amorphous MnO2 yielding an additional capacity at cell voltages above
1.7 V. However, as the half-cell reaction involves H+ and shifts the pH at
the cathode, cell design has to deal with zinc hydroxide sulfates pre­
cipitation during charging [188].
6.2.2Vanadium oxides and phosphates
Vanadium compounds offer a similar diversity as manganese dioxide
compounds due to their versatile crystal structures. The broad range of
oxidation states leads to an extensive toolbox of possible cathode
structures. As with manganese oxides, many vanadium compounds, such
as vanadium pentoxide (V2O5), have been investigated as cathode ma­
terials for lithium-ion batteries for more than 40 years [193]. Various
compounds were successfully tested as a zinc host material in mild acidic
electrolytes [7]: vanadium oxides, such as V2O5 and V3O7, with different
stoichiometric combinations or polymorphs [194], metal vanadates,
such as MxV3O8⋅H2O or MxV2O7⋅H2O (with M = Na, Ca, Fe, or Zn)
14
Journal of Power Sources xxx (xxxx) xxx
[195–199], and vanadium phosphates like Na3V2(PO4) [200]. A layered
structural framework, which allows reversible intercalation at high ca­
pacities, is typical for almost any vanadium compound. Practical ca­
pacities exceed the typical capacities of manganese oxides of 300 mAh
g− 1. However, the low average voltage of 1V limits the energy density of
vanadium compounds.
Insertion of water into vanadium oxides is reported to significantly
influence the cathodic charge storage process [201–203]. The Nazar
group [203] demonstrated a significantly higher capacity for the hy­
drate V3O7⋅H2O in aqueous electrolytes than in nonaqueous electrolytes.
This demonstrates the importance of hydration for zinc intercalation.
Similar results hold for the hydrate V2O5⋅H2O [204], where the capacity
diminished, after the structural water was removed by ex-situ heating of
the cathode. DFT calculations for V2O5⋅H2O rationalize that interlayer
water improves the diffusion of multivalent ions, reduces the interca­
lation barrier, and increases the interlayer spacing [201].
The long-term stability of vanadium compounds remains a chal­
lenge. Vanadium dissolution and instability of the layered structure are
the key degradation processes. Vanadium can electrochemically dissolve
in aqueous electrolytes, thereby altering electrolyte pH and inducing the
formation of solid byproducts. This degradation process depends solely
on time such that cycling stability at low rates appears inferior [205],
but capacity retention at very high currents appears excellent. On the
one hand, the large interlayer spacing of the layered structures allows
for low insertion barriers, on the other hand it endangers the structural
stability during inhomogeneous insertion of zinc. Pre-intercalated
compounds acting as “pillars” for the structure can mitigate this effect
[7]. Analogous to vanadium oxides for lithium insertion [206], metal
cations, for example, can achieve this pillaring effect. Nanostructuring
of the cathode allows for further mechanical stress reduction due to the
high specific surface [119].
The charge storage mechanism for vanadium compounds is less
debated than for manganese oxides and appears to be pure zinc
N. Borchers et al.
intercalation. For metal vanadates, however, the simultaneous interca­
lation of Zn2+ and H+ was reported [207]. Not surprisingly, ex-situ XRD
data reveal the formation of Zn4SO4(OH)6⋅H2O as byproduct. Another
reaction worth mentioning is the reaction mechanism observed in pillar
structured transition metal vanadates, such as Ag0⋅4V2O5 [208]. Here,
the proposed mechanism is both a replacement of the transition metal
with zinc ions and zinc insertion into the newly formed phase.
6.2.3. Prussian blue analogs
Prussian blue analogs (PBAs) are host materials for a broad range of
metal ions. The cubic metal-organic compounds feature wide interca­
lation channels with fast ionic conductivity. Among the PBAs, metal-
hexacyanoferrates (HCF) are the most promising candidates which are
suitable host materials for both mono- as well as multivalent ions [209].
For zinc-ion batteries, a reversible intercalation process was shown for
ZnHCF and CuHCF in aqueous ZnSO4 electrolytes [210–212], as well as
for FeHCF [213,214] in a bioionic liquid-water electrolyte. Except for
FeHFC, the PBAs feature very high cathodic potential. At 1.7 V vs.
Zn/Zn2+, the potential is close to the oxygen reduction reaction in
aqueous electrolytes. Despite their excellent utilization of the electrolyte
stability window, the low specific capacity of all compounds, which is
around 60 mAh g-1, is inferior to manganese and vanadium compounds.
The electrochemical behavior of PBAs is shown to depend on the
exact structural properties. For ZnHCF, Zhang et al. report different
capacities for the structural polymorphs [211]. Additionally, their
measurements indicate that surface orientations might change with the
dissolution of the PBA. Adding to this observation, Yang et al. observed a
pH-dependent cyanide dissolution driven by ligand exchange with hy­
droxy groups [215]. Interestingly, the stability of metal hex­
acyanoferrates depends on the used electrolyte with stable cycling in
ZnSO4 electrolyte but rapidly decreasing capacity in Na2SO4 and K2SO4
electrolytes [215].
6.2.4. Organic cathodes
While manganese, vanadium, and PBA cathodes are well-studied
materials, more unconventional cathode materials feature exciting
properties. Organic cathodes are sustainable and lightweight, which
implies a high specific capacity. Their low cost and excellent electro­
chemical tailorability, makes them very attractive. The benzene de­
rivatives quinones are already used in aqueous batteries. Yet, there are
only a few studies for zinc-ion batteries [216–218]. Zhao et al. [216]
resented particularly astonishing work on a Calix [4]quinone (C4Q)
cathode, which achieved a high capacity of 335 mAh g− 1. The charge
storage mechanism is based on the reduction of carbonyl groups, which
leads to several active sites per molecule. Nevertheless, the quinones
have a low conductivity, creating the need for conductive additives.
Another capacity-limiting aspect is the solubility of quinone salts of type
ZnxC4Q. While the quinone itself has astonishingly low solubility, the
cathodes discharge product can dissolve, which not only decreases
cathode capacity, but might also lead to degradation of the anode [216].
Transition metal dichalcogenides, for example, VS2 or Mo6S8 [219,
220], were also tested as cathode material. Besides their layered struc­
ture with weak intralayer-bonds, there is no clear advantage compared
to manganese and vanadium compounds, as Tang et al. [221] conclude.
6.2.5. Aqueous electrolytes
Aqueous electrolytes, which are used for most zinc-ion batteries,
offer several advantages, such as higher conductivity, a lower price
point, non-flammability, and environmental safety, when compared to
organic electrolytes of lithium-ion batteries. Nevertheless, challenges
with respect to reaction kinetics and electrochemical stability remain.
In aqueous electrolytes, the pH stability and complex formation
varies among different salts and determines electrolyte performance.
Zn2+ does not only coordinate with water in aqueous solutions but forms
various zinc complexes. For example, in zinc sulfate electrolytes, zinc is
mainly found in the charge neutral ZnSO4 complex and to a smaller
15
Journal of Power Sources xxx (xxxx) xxx
extent in negatively charged sulfate complexes [222]. Zinc speciation
depends on total concentration of dissolved zinc and electrolyte pH. If a
significant amount of zinc is bound in neutral or even negatively charged
species, the effective transfer coefficient of zinc is decreased. During
discharge, zinc concentration increases in the zinc electrode and de­
creases in the cathode. This constitutes an imbalance in availability of
Zn2+ at active sites during cycling. As zinc speciation leads to inhomo­
geneous electrolyte pH, it affects the stability window of the electrolyte
and the parasitic reactions at both anode and cathode.
The first study on different neutral and mild acidic electrolytes with
electrolytic MnO2 cathodes was performed in 1988 [180]. The tested
zinc salts, such as ZnCl2, Zn(NO3)2, ZnSiF6, and Zn(PF6)2, all showed
reversible reaction mechanisms, but ZnSO4 showed the best result.
While ZnSO4 is still the most common salt for near-neutral zinc-ion
batteries, the aqueous Zn(CF3SO3)2 electrolyte proposed by Zhang et al.
gains attention [223]. It is increasingly employed in recent studies,
especially for vanadium compounds [7]. The triflate ion (CF3SO−3 ) is
bulky, which influences the electrochemical and transport properties of
the electrolytes [224]. In the case of aqueous solutions, positively
charged Zn2+ is predominant as the triflate ion is completely dissociated
[225]. Similar results can be found in studies for Zn (TFSI)2 [197] and Zn
(ClO4)2 [226], where both the TFSI and the perchlorate ion are known
for not forming complexes with cations in aqueous solutions. The
prevalence of non-complexed zinc is favorable for the charge transport
between the electrodes. In contrast, in zinc sulfate-based electrolytes,
neutral or negatively charged zinc sulfate and hydroxide complexes
make up most of the electrolyte.
The zinc speciation in the electrolyte determines the charge transport
processes between the electrodes, affects the dendritic zinc deposition,
and interferes with the reaction mechanism of the cathode [135].
Furthermore, zinc complexes were shown to have a crucial influence on
dendritic growth and deposition behavior at the anode and intercalation
processes at the cathode [227]. For manganese oxides and vanadium
oxides, several charge storage processes are proposed, which include, at
least partially, H+ ions. These processes critically influence the local pH
and speciation at the interface, which leads to the formation of solid
by-products [158]. Electrolyte additives, such as buffering agents or
corresponding acids, as well as other inorganic zinc salts are extremely
cost-efficient ways to improve performance and stability and were
already successfully validated for rechargeable zinc-air batteries [68,
69].
Zinc electrodes operate outside the theoretical electrochemical sta­
bility of water, which can lead to hydrogen gas evolution especially at
acidic near-neutral pH values. Super-concentrated solutions of water
and zinc salts have been proposed to widen the electrochemical stability
window of aqueous electrolytes. So-called water-in-salt electrolytes alter
the solvation properties of dissolved zinc species. Creating an environ­
ment in which the concentration of Zn(II) complexing ligands is high
enough to stop the central zinc ion from coordinating with H2O, the
transport of water to the electrode surface can be significantly reduced.
As a result, the electrode can operate at potentials far below the equi­
librium hydrogen evolution potential without evolving H2 gas.
Wang et al. performed molecular dynamics simulations of concen­
trated Zn (TFSI)2 + LiTFSI electrolytes to examine the mechanism for the
observed increase in the electrochemical stability window [227]. Their
simulations show that the coordination number of Zn with H2O in 5 m
electrolyte solutions is circa 6. As the concentration increases to 10 m
and 20 m, the coordination number with water falls to circa 4 and 0,
respectively.
6.2.6. Non-aqueous electrolytes
Aqueous electrolytes have a clear cost, safety, and environmental
advantage, but they are limited by the voltage stability window of water
which limits the practical cell voltage of aqueous zinc batteries to 1.7 V
or less, favors self-discharge, and lower coulombic efficiencies [178].
Organic electrolytes can extend this voltage window to 3–4 V vs
N. Borchers et al.
Zn/Zn2+ and reach self-discharge rates and coulombic efficiencies on
par with Li-ion batteries (>99%) [224]. However, the zinc-ion batteries
using organic electrolytes are at much lower technology readiness level
(TRL) than their aqueous counterpart and their performances are much
weaker for several reasons detailed below.
The US-DOE Joint Centre for Energy Storage Research published
experimental results and DFT calculations [224] which compared the
properties of different electrolytes for organic Zinc-ion batteries.
Acetonitrile-Zn (TFSI)2 was found to be the most stable solvent with a
voltage window of 3.8 V vs Zn/Zn2+ on a platinum electrode followed by
propylene carbonate, DMF and diglyme from most stable to least stable.
The stability to oxidation is limited by the TFSI− anion for MeCN and PC
whereas the solvent is oxidized before the TFSI− anion in DMF and
diglyme.
The highest conductivities are obtained with 0.5 M Zn(TFSI)2, for all
solvents. At higher concentrations conductivity is not increased in
contrast to lithium-ion conductivities in the same solvents. However, the
solubility of the zinc salts which may not be high enough to reach 1 M.
Acetonitrile and TFSI− give the highest conductivities, which are
attributed to less coordinated solvent molecules and more dissociated
anions. The DFT calculations suggest that factors affecting the dynamics
of ions are viscosity, dielectric constant, donor atom of the solvent,
molecular geometry, and the strength of interactions with cations and
anions. The best conductivities obtained are still 2–3 orders of magni­
tude lower than for aqueous electrolytes, the highest conductivities have
been obtained with 0.5 M Zn(TFSI)2 in acetonitrile at 28 mS cm− 1 at
room temperature [224]. The lowest zinc deposition overpotentials are
obtained at the highest concentrations (1 M). Very low zinc plating
overpotentials are obtained with 1 M Zn(TFSI)2 in propylene carbonate,
down to 20 mV, and it increases to 50 mV when switching to MeCN at
the same concentration. From this JCESR study, the solvent of choice for
the electrolyte therefore appears to be acetonitrile, which is also the one
most widely used, and the best electrolyte appears to be 0.5 M Zn (TFSI)2
in acetonitrile.
Organic electrolytes have been tested with zinc intercalation mate­
rials such as vanadium polyanion-type phosphates [228] and bilayered
hydrated V2O5 [229], prussian blue analogue compounds [230],
substituted ZnCo2O4 spinels [231,232], δ-MnO2 [233] and transition
metal sulfides [234].
The kinetics of zinc-ion batteries have been found to be much more
sluggish in organic electrolyte compared to the aqueous electrolyte,
adding charge transfer resistance to the already slow solid-state diffu­
sion of the zinc ion. In a study comparing the performance of a layered
V3O7⋅H2O cathode in aqueous (1 M ZnSO4 in H2O) and organic (0.25 M
Zn(CF3SO3)2 in acetonitrile) electrolyte [229], the interfacial charge
transfer resistance was found to be up to 100x higher in organic elec­
trolyte. The activation energy at the cathode was also found to be 3x
higher. This is attributed to facile desolvation and suppressed electro­
static repulsion between zinc ions by shielding with H2O in aqueous
electrolyte. The rate capability and practical areal loading of these
batteries will therefore be severely impacted compared to their aqueous
counterpart. High C rates are only obtained at very low areal capacities.
For example, 20C rates was obtained on a Zn/V2O5 battery using 0.5 M
Zn (TFSI)2 in acetonitrile [229], but at very low areal capacities (0.54
mAh cm− 2) which are far from what would be needed in a practical
battery.
A study of zinc electrodeposition in a Zn(CF3SO3)2/acetonitrile
electrolyte using ultramicroelectrodes and COMSOL simulations
concluded that the reduction occurs as a simple one step two− electron
reduction mechanism [235] in contrast to Mg2+ which requires a more
complicated multi-step pathway with a higher activation barrier, sug­
gesting organic zinc-ion batteries might by easier to master than mag­
nesium secondary batteries.
16
Journal of Power Sources xxx (xxxx) xxx
6.3. Outlook
Many cathode materials have successfully been tested within zinc ion
batteries, showing stable cycling behavior and promising cathode ca­
pacities. However, the charge/discharge mechanisms of these cathodes
are still under debate. Improved mechanistic understanding will allow
clearer goals for materials research. Furthermore, the research on zinc
metal anodes for zinc ion batteries is not as advanced as their counter­
parts in zinc air batteries.
Often overlooked in current research is the contribution of the
electrolyte to the charge storage reactions and its influence on cell
performance. There are only few studies on the applicability and
behavior of zinc salts besides ZnSO4 and ZnOTf2. But the advantages of
tailored electrolytes are numerous. Both the dissolution/precipitation of
manganese or vanadium, as well as the formation of solid by-products
are tightly linked to pH stability and diffusion limitations of the elec­
trolytes. At the same time, electrolyte design is an efficient way of
boosting performance. It is reducing overpotentials, increase zinc
transport properties in the electrolyte, achieve a more compact zinc
morphology and stabilize the cathode materials.
Let us highlight key benchmarks [236] that should be addressed by
further research. High-rate cycling over short times often looks great,
but studies should also state low-rate cycling to evaluate long-term
stability. Capacities should be evaluated over several cycles as the ca­
pacity of the first cycle is often influenced by side reactions. Some
studies report practical capacities that contradict the proposed reaction
mechanisms. Theory and model should be included to resolve such a
paradox. The key question is how many electrons are transferred per
zinc-ion and per cathode unit cell. Furthermore, we suggest building full
cells wherever possible. This would clarify if the proposed concepts
work for reasonable ratios of cathode, anode, and electrolyte mass.
7. Outlook
In this review, we have summarized the status of current research on
zinc batteries. The zinc metal electrode is the common element among
all zinc cell designs as it enables competitive energy densities at low
cost. Hydrogen evolution, electrode shape-change, and zinc deposition
morphology remain important challenges for materials research. The
goal of current research should be to achieve better cycle life at large
zinc utilization and high loadings to bring the cost down beyond that of
Li-ion technology. This can be addressed by zinc electrode design, by
mixing additives into the zinc electrode materials, and by designing the
electrolyte.
The zinc metal electrode is compatible with aqueous electrolytes.
This constitutes the key advantage of zinc batteries. Zinc-air batteries,
nickel-zinc batteries, and primary alkaline batteries use strongly alka­
line electrolytes with hydroxide as main charge carrier and zincate as
dissolved zinc species. Modern zinc-ion batteries as well as new gener­
ation zinc-air batteries rely on near-neutral electrolytes with neutral or
positive zinc complexes as main charge carrier. This demonstrates the
tunability of aqueous electrolytes that can be adjusted to improve zinc
deposition and the cathode reaction mechanisms. Electrolyte additives
have been shown to improve zinc deposition morphology and reduce
hydrogen evolution. However, further research is necessary to reach the
design goals. An alternative approach is to develop new electrolytes
based on polymers or organic salts. In this way, limitations of the pos­
itive electrodes, e.g., carbonate formation for zinc-air batteries and co-
intercalation for zinc-ion batteries can potentially be resolved. Non-
aqueous electrolytes promise high electrochemical stability and higher
cell voltages, but they cannot yet deliver the performance of aqueous
electrolytes. We note, however, that concentrated organic salts in
aqueous electrolytes or admixture of water to ionic liquids constitute an
important field for further research.
The gas diffusion electrodes for zinc-air batteries are very mature. A
lot of research is directed at improving the cycling life of demonstrators
N. Borchers et al.
and the power density with efficient bifunctional catalysts on the ma­
terials level. Here, we want to motivate the development of clear
benchmarks. Cathodes for zinc-ion batteries are less well understood.
Therefore, more research is needed to rationalize the reaction mecha­
nisms and find a combination of electrolyte and cathode materials that
provides long-term stability and high energy densities at low cost.
We emphasize that research should have the whole battery cell under
the condition of applications in mind, even in the case of fundamental
materials research. It happens too often that individual aspects are
addressed with specific solutions that neglect the overall cell concept.
For example, most of the results reported in the literature focuses on the
positive half-cell with a thick zinc foil which is partly consumed during
battery cycling. Measurements are also reported with low positive
electrode loadings, far from what would be required in a commercial
cell, thus making extrapolation to a real system difficult. Furthermore,
electrolyte degradation and consumption can be overlooked if a surplus
of electrolyte is present in lab cells. Temperature is also a parameter
which does not receive enough attention. Cells are very rarely tested
above room temperature. As most applications will require the cells to
be able to operate up to 60 ◦ C without harm, the impact of slightly
higher temperatures needs to be investigated. Self-discharge is another
parameter not to be overlooked. If results are reported at high C rates
only, the effect of self-discharge is masked. We suggest that studies for
newly proposed concepts should aim for tests under realistic conditions.
Wherever possible, the test parameters, such as cycling rate and cell
design, should match the envisioned application. Multi-scale modelling
can help to accelerate and improve these tests.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The work of B. Horstmann and N. Borchers was supported by the
German Ministry of Education and Research (BMBF) under Project ZIB
03XP0204F. This work contributes to the research performed at CELEST,
SINTEF AS and EDF R&D.
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