Materials Today Advances 6 (2020) 100046

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On battery materials and methods

R. Borah a, F.R. Hughson b, J. Johnston a, T. Nann a, *
a
The University of Newcastle, School of Mathematical and Physical Sciences, Callaghan, NSW, 2308, Australia
b
Victoria University of Wellington, School of Chemical and Physical Sciences, Kelburn Pde, Wellington, New Zealand

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

Article history: Economical and efficient energy storage in general, and battery technology, in particular, are as imper-
Received 18 September 2019 ative as humanity transitions to a renewable energy economy. Rare and/or expensive battery materials
Received in revised form are unsuitable for widespread practical application, and an alternative has to be found for the currently
5 December 2019
prevalent lithium-ion battery technology. In this review article, we discuss the current state-of-the-art of
Accepted 11 December 2019
Available online xxx
battery materials from a perspective that focuses on the renewable energy market pull. We provide an
overview of the most common materials classes and a guideline for practitioners and researchers for the
choice of sustainable and promising future materials. In addition, we also discussed the best practice for
Keywords:
Anode
battery performance testing and reporting.
Cathode © 2019 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
Electrolyte license ([Link]
Battery
Lithium
Materials

1. Renewables story However, there are times when the sun doesn't shine, and the
wind doesn't blow. This is why energy storage is needed, in order to
In 1959, global CO2 levels were at 313 parts per million (ppm). provide renewable energy during these low production or high
Now, just six decades later, they are 100 ppm higher, recently demand times, and also limit the wasted energy from renewable
surpassing 412 ppm in September of 2019 [1]. This is an unprece- generation curtailment, which is becoming increasingly prevalent
dented change in atmospheric conditions, which effect is already as renewable generation increases. Pumped hydropower has pro-
having, and will increasingly have a major impact on the Earth in vided the cheapest form of energy storage in the past, with more
the decades to come [2]. Despite advice from climate researchers to recent projects ranging from $3.35 M to as low as $0.39 M per MWh
reduce this dangerously rapid rise in greenhouse gas emissions for the addition of a pumping system to existing dams, the mean of
because of the uncertainty in the upper “safe” boundary [3], hu- these being about $1.8 M/MWh [6]. Pumped storage also has the
manity continues to release roughly 40 billion tons of CO2 into the added benefit of being more suitable for long term and general bulk
atmosphere every year [4]. This is primarily an economically driven energy storage. However, pumped hydropower has geographical
phenomenon, as fossil fuels have proven to be a relatively cheap limitations, namely a difference in elevation, which is not available
and reliable form of energy. However, change is afoot. According to in all locations. Electrochemical storage on the other hand is much
Bloomberg New Energy Finance's 2019 New Energy Outlook, more suitable for maintaining an uninterrupted power supply and
renewable energy technology like solar and wind are already un- providing load shifting. These are both important requirements
dercutting the cost of fossil fuels in two-thirds of all locations, and with an increasing renewable generation [7]. These factors, along
by 2030, it will be cheaper to generate from renewable sources with Li-ion batteries plunging 85% in cost since 2010, to $187/kWh
almost everywhere [5]. We need this transition to happen as in March 2019, is why electrochemical storage has gained in
rapidly as possible if we are to prevent positive feedback effects and popularity in recent years [8].
prevent the worst effects of climate change. A recent study by Stock et al. [9] that looked specifically at the
Australian energy landscape found that the country did not need
significant amounts of new energy storage until roughly 50%
renewable energy generation is reached. However, beyond 50%
renewable energy generation, the amount of storage required in-
* Corresponding author.
E-mail address: [Link]@[Link] (T. Nann).
creases significantly. Sisternes et al. identified that the “diminishing

[Link]
2590-0498/© 2019 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license ([Link]
2 R. Borah et al. / Materials Today Advances 6 (2020) 100046

marginal value of energy storage means that the economically Compounds with fluoride in it are very often toxic; however, due to
optimal penetration level of storage will be limited unless costs fluorine's abundance and usefulness in electrolytes due to its sta-
continue to decline well beyond current targets” [10]. This scenario bility against oxidation, it has and will likely continue to play a
is likely similar to other nations. As such, we need versatile and major role in batteries.
economically desirable forms of energy storage in order to bridge When choosing a metal for use in a battery, there are a number
the latter half of the climb toward a 100% renewable economy and of considerations to take into account. Lithium only comprises
combat against the worst effects of climate change. We have until roughly 0.002% of the Earth's crust [16,17]. Any of the remaining
roughly 50% renewable generation to find and scale these solutions. groups of one or two metals underneath lithium in this adapted
The clock is indeed ticking. periodic table are tens to thousands of times more abundant while
providing nearly as negative reduction potential, all between
2.37
2. A first principles approach and
2.93 V vs. the standard hydrogen electrode (SHE) compared
to lithium's
3.04 V. This figure is important for achieving high
The energy storage market can be broadly split into two sectors: voltages in cells; the more negative the standard reduction po-
stationary and mobile. The stationary storage sector is purely tential of the metal, the higher the voltage that the cell can theo-
interested in a cost per unit of energy ($/kWh) figure. Of course, retically have. Lithium will likely dominate the market over the
safety is important too, but this is captured within the $/kWh figure next 5e10 years or so, but as demand for storage soars and lithium
of merit, as more dangerous solutions require more rigorous safety supplies dwindle, we will increasingly need to look at alternatives.
systems, which increase the cost. This is part of the reason why, in Leisegang et al. [18] tried to quantify the electrochemical and
principle, nuclear power is cheap, but in practice, it is expensi- economic benefits of each battery type, with the less well-known
veddue to the high cost of safe construction [11]. Mobile storage, aluminum-ion coming out on top, due to its high theoretical
on the other hand, needs to factor in the energy density. It is volumetric energy density and being the most abundant metal in
impractical to have a one-ton battery powering a three-ton vehicle. the Earth's crust.
Therefore a cost per energy density, kWh=kg $ , figure is appropriate.
Mobile storage is an area perhaps more interested in inherently safe 3. Battery components
systems, due to the impact of the weight of additional safety
structures, as well as the additional cost. Generally speaking, a battery consists of five major components.
An anode, cathode, the current collectors these may sit on, elec-
2.1. Tools for low-cost batteries trolyte and separator, as shown in Fig. 2.
The purpose of the anode is to hold the active ions in a high
Battery engineers have two broad strategies to achieve low-cost energy state. The higher the energy state, the higher the eventual
cells. Materials and morphology. Low cost, abundant materials that voltage of the cell. In principle, pure metal is the best anode ma-
can be economically engineered into the appropriate form are terial, due to the metal being the highest possible energy state to
required for low-cost cells. Therefore, any fabrication process that is hold the metal in, as well as holding the largest amount of metal
itself inherently expensive, despite using abundant materials, must atoms in the smallest amount of space. However, dendrite forma-
be excluded when engineering low-cost cells. However, materials tion often hampers the use of pure metal. Hence, other solutions,
that currently have a high production cost but are made out of which can prevent this dendrite formation, are often used instead,
abundant materials of the Earth, such as carbon nanotubes (CNTs), such as inserting the ions into the interlayer spacings in graphite.
may start to become economically enticing as production econo- Conversely, when the metal is oxidized and the resultant ion moves
mies of scale are reached in the coming years. Although currently over to the cathode during discharge, the ion inserted cathode
expensive, methods of producing and sorting various types of CNTs needs to be in a much lower energy state than when it was at the
are attracting huge research attention [12,13], and hence, prices on anode. It is this difference in energy that gives the thermodynamic
the order of $100/kg are anticipated in the future for multi-walled push for electrons to move through a circuit and do work. The
CNTs [14]. Fig. 1 shows the materials that are available for the larger the difference, the higher the voltage, and the battery will
production of a low-cost cell. store more energy.
Currently, the battery industry is taking strides to move away The electrolyte soaked separator must help facilitate this ionic
from cobalt, due to its cost and ethical issues associated with its movement while being electrically insulating in order to prevent
production [15]. Therefore, elements already more expensive than short-circuiting. They should also be spectators on the electro-
cobalt were excluded outright. The materials that are comparable chemical stage. If they do participate, they will be rapidly
in rarity or are currently cheaper but also rarer than cobalt are decomposed and/or coat either electrode in a solid electrolyte
lightly crossed out with green. These elements may play some part interphase (SEI), which can impede ionic movement, thus
in the batteries in a renewable economy, but only the noncrossed degrading the cell. The electrolyte can be engineered with additives
ones show promise for a truly supply unconstrained battery. in order to form stable ionically conductive SEIs [19e21].
However, chromium and vanadium may not be entirely supply
unconstrained, as they are only roughly three to four times more 4. Mechanisms
abundant than cobalt [16,17]. Finally, the marginally toxic elements
like vanadium, chromium, and fluorine are lightly crossed out with An ion-battery operates by transferring charge using freely
red, due to the health concerns when dealing with these elements. moving ions shuttling back and forth between the two electrodes.
These environmental consideration of these elements needs to be This charge transfer occurs via different mechanisms depending on
on a case by case basis; V2 O5 , the most common oxide of vanadium, how the active ion interacts with an electrode material. The amount
is environmentally toxic, while VO2 is merely an irritant. In some of charge that a battery can store depends on the potential differ-
countries, chromium use has particular health regulations in place ence of the electrochemical reactions of the active ion that occur at
due to the presence of trace amounts of Cr(VI), which is a carcin- the two electrodes and the number of electrons involved in each of
ogen. While it would be ideal to avoid the toxic compounds alto- these reactions. One can either increase the potential difference
gether, if they showed enough promise, then they would still be between the two electrode processes or use ions involving multiple
commercially viable options. Fluorine demonstrates this perfectly. electrons to increase the amount of charge stored or the capacity of
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 3

Fig. 1. The periodic table for cheap, safe batteries.

electrode (SHE) has been one of the primary motivations behind

the development of Li-ion batteries. In general, for any active ion
Mnþ , plating and stripping at the metallic M electrode generates
maximum theoretical capacity, 3860 mAh/g in the case of Liþ =Li.
However, with great reduction potentials come great reactivity.
Operating with a highly reactive Li metal electrode is a risky busi-
ness. Even if the sensitivity to O2 and moisture is controlled, the
reactive metal surface suffers from the formation of dendritic Li,
which, in turn, leads to the shorting of the cells [22]. These aspects
have been discussed for post-Li-ion systems in detail in Section 6.1.
Despite significant benefits, plating and stripping of Mnþ= M sys-
tems have often been replaced with intercalation-deintercalation
systems, for example, graphite intercalation compounds (GICs).
Although the theoretical capacity for GICs is much lower compared
to the metal anode, the slightly more positive potentials of such
compounds help avoid dendrite formation in most cases [23].

4.2. Intercalation-deintercalation

Intercalation of ions into layered materials, such as graphite or

transition metal chalcogenides, has been extensively used as a
charge transfer process in ion batteries [24e26]. Insertion/extrac-
Fig. 2. A typical cell format. Charging processes are indicated in green, and discharging tion of ions in the interlayer spaces of such layered structures
processes are indicated in red. On discharge, the high potential metal atoms oxidize, usually results in no structural change in the host structure other
and the resultant ions move toward and interact with the reducing cathode. than disruption in the interlayer spacing (usually an increase in the
van der Waals gap) [27]. In such a case, the ion is said to have
intercalated into or deintercalated from the layered structure. The
the system. Both these factors are governed by the mechanism with
energy change involved with intercalation and thereby the
which charge is transferred. The following sections discuss the
disruption of the layer spacings is mediated by charge transfer
common mechanisms of charge transfer in ion batteries.
between the host ion and the guest structure, usually a redox
process. In the case of layered materials, such as graphite, redox
4.1. Electroplating-stripping reaction upon intercalation involves the p-electrons of the material
[28]. In the case of transition metal chalcogenides, the redox re-
The highly negative reduction potentials of alkali and alkaline action involves the transition metal center. These two types of
earth metals have always been electrochemical processes of choice intercalation-deintercalation processes are well exemplified by the
to capitalize on for high voltage systems. The low reduction po- LiCoO2-graphite system introduced by Goodenough and co-
tential for the Liþ/Li system at
3.04 V vs. the standard hydrogen workers in 1980 [29].
4 R. Borah et al. / Materials Today Advances 6 (2020) 100046

During charging, Liþ ions are removed from the LiCoO2 cathode cycling stability and high-voltage hysteresis resulting in low effi-
and intercalated into the graphite anode. This movement of Liþ ions ciency [24]. Conversion reactions based on the oxidation/reduction
results in the oxidation of Co(III) centers in the cathode to Co(IV) of the anionic species do not require the TM and can be generalized
and the reduction of graphite at the anode. The oxidation of Co(III) by the following reaction;
to Co(IV) is a thermodynamically unfavorable process, and the large
potential difference of it against the reduction of graphite upon Liþ X þ aLiþ þ ae
#Lia X
ion insertion results in the large cell voltage. Thus, the high
The chalcogens (O, S, Se, Te) and the heavier halogens (Br, I)
oxidation potential of a transition metal center is exploited by using
undergo conversions of this type to form Li2 X and LiX, respectively
intercalation/deintercalation of ions to generate high cell voltages.
[33]. Such conversions have high theoretical capacities, for
Although intercalation mechanisms have proven to be a reliable
example, 1672 mAh/g for LieS systems. However, the poor con-
way of storing charge with a decent capacity and good cyclability, it
ductivity of elemental sulfur and the related sulfides, and dissolu-
is rather inefficient in terms of atom economy. Lithium dein-
tion of the polysulfide species affect efficiency and cyclability
tercalation in LiCoO2 is reversible only to up to Li0.5CoO2 [30].
drastically [35].
Therefore, for every unit charge stored reversibly, we need two Co
atoms and four O atoms. This results in lower specific capacities of
intercalation electrodes, especially for electrodes, such as LiCoO2 , 4.4. Alloying
which are limited by the growing prices of Co.
Moreover, intercalation/deintercalation of larger guest ions, Another mechanism of charge transfer, alloying, can be seen as a
such as Naþ and Kþ , or multivalent ions, such as Mg2þ or Al3þ is not variation of the conversion mechanism, the difference being,
as straightforward as that for Liþ [31]. For example, Naþ interca- instead of forming a chemical species LiaY, a lithium alloy LieY is
lation into graphite is negligible [25,32] and multivalent ions have formed. Alloying materials, preferably having low de-lithiation
poor mobility in most layered frameworks due to their higher potentials, are mostly used in anodes. Si, Sn, and Sb are the most
charge density. extensively studied alloying anodes for Li-ion batteries [23]. For
These shortcomings of intercalation/deintercalation mecha- example, a Si anode can alloy Li with the stoichiometry of Li4.4Si,
nisms have led researchers to look for other processes to achieve leading to a capacity of around 4200 mAh/g. However, alloying
higher capacities. To obtain higher capacities, one has to involve reactions suffer from a similar flaw to conversion reactions, a
more electrons per atom in the redox processes. However, such drastic transformation of the electrode material. In this case, the
processes usually change the chemistry and structure of electrode electrode material undergoes a large volumetric expansion. Lith-
materials largely, thereby affecting reversibility. iation to the extent of Li4.4Si (Li22 Si5 ) is accompanied by volume
expansion of 300% [36]. Silicon electrodes are further discussed in
6.1.6.
4.3. Conversion Volume changes of such severe magnitudes often crack the
electrode material, leading to loss of contacts, loss of active mate-
A conversion mechanism involves electrochemical reactions rial, disruption of the solid electrolyte interphase (SEI) resulting in
that are leading to the formation of new chemical species, often electrolyte decomposition (see Section 6.2.1). Even if the lithiation
with structures different from the initial structure. For example, a is controlled to Li3.75Si (Li15 Si4 ) the volume expansion is still sig-
conversion reaction for a Li-ion system can be represented as nificant (290%) [37,38]. Alloying materials are often made into
follows: composite structures to accommodate expansion and increase
conductivity, for example, as composites of porous carbons, gra-
Ma Xb þ ðb , cÞLiþ þ ðb , cÞe
#aM 0 þ bLic X phene, CNTs, etc. However, the addition of high surface area
carbonaceous materials often leads to a pseudocapacitative
where M is a transition metal (TM), X is an anionic species, for
behavior. Although strategic nanostructuring can help to avoid
example, oxide, fluoride, or sulfide. Unlike in the case of interca-
pseudocapacitance, these additives lead to a loss in specific ca-
lation mechanisms, the TM center is reduced to zero oxidation
pacity compared to the pristine material and also add to the cost.
state, thereby involving more redox electrons, and thus, a larger
theoretical capacity [33].
The first report for a conversion-based Li-ion battery was from 4.5. Pseudocapacitance and surface mechanisms
Tarascon and co-workers in 2000, where they reported a series of
transition metal oxide nanoparticle-cathodes with capacities of up In order to resolve the expansion issues in alloying electrodes,
to 700 mAh/g over 100 reversible cycles [34]. The system was based many groups have resorted to nanostructuring of electrode mate-
on the formation and decomposition of Li2 O from Liþ ions aided by rials. However, high surface area electrode materials or composites
the reduction and oxidation of the TM center, respectively. are not always ideal battery materials. High surface area materials
Following are the reactions: tend to exhibit pseudocapacitative behavior. Pseudocapacitance
can be seen as an intermediate case between bulk redox in crys-
discharging talline materials and surface-induced capacitance in layered ma-
Cathode : CoO þ 2Liþ þ 2e
) * Co0 þ Li2 O
terials. Pseudocapacitance is a faradaic process, however it involves
charging
discharging redox reactions at surface sites, which are usually disordered. In
Anode :2Li ) * 2Liþ þ 2e
common battery materials, redox reactions occur uniformly across
charging
a crystalline phase, and thereby, at the same potential. On the other
By returning to the concept of atom economy, for the same hand, as surface redox sites are nonuniform, pseudocapacitative
transition metal, the conversion mechanism draws two unit charge transfers occur within a range of potentials, thereby
charges per cobalt atom as opposed to one per two Co atoms in the exhibiting a sloped charged-discharge characteristic or broad, ill-
intercalation/de-intercalation mechanism. However, the higher defined peaks in cyclic voltammetry [23]. Such materials increase
capacities come at the cost of transforming the electrode material, the rate capability as the surface involvement reduces the solid-
which results in numerous drawbacks, such as low conductivity of state diffusion lengths or even have diffusionless transformations.
the resultant electrode species, volume expansion leading to poor Notable here is the report by Grimaud, wherein the surface of a
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 5

MnOeLiF composite undergoes a diffusionless phase trans- The total capacity of an ion battery is influenced by both the
formation through which Liþ ions can be reversibly exchanged [39]. capacity of the cathode and the anode. Mixed ion batteries can get
Such surface-based conversions can have the benefit of tuning the around the problem of having to find a high capacity anode and
capacity by controlling the particle size or morphology, and cathode for the same ion and allow researchers to cherry-pick high-
thereby, the surface availability. However, such processes are still performance electrodes individually.
conversions and will come with the associated disadvantages. One Since the initial report, several similar systems based on other
specific drawback is the electrolyte decomposition that occurs cations, such as Kþ and Mg2þ have been reported [47]. Such sys-
when the solvent is oxidized at the surface at high potentials. In tems can be seen as alternatives to Liþ ion batteries for which we
general, while dealing with new nanostructured electrode mate- are closing in on resource limitations.
rials, it is advisable to consider pseudocapacitance and surface
mechanisms especially, because this classification is important 4.6.3. Dual-ion batteries
from an application perspective. Although the intercalation of anions into graphite has been
known since the 1930s [28], only since the 90s anions were used as
4.6. Conventional, dual-ion and mixed-ion batteries active species in batteries. Carlin et al. [48] developed dual-graphite
batteries with various molten salts of imidazolium cations and




While traditional ion batteries are based on cationic active anions, such as PF


6 , BF4 , AlCl4 , CF3 SO3 , and C6 H5 CO2 . Since then,
species, progress in research has led to the development of systems such batteries that employ both anions and cations of an electrolyte
based on or involving anionic active ions. More unconventional as active species have been developed, which have now become
systems, such as the dual-ion or mixed ion batteries, have also popular as dual-ion batteries. Considering the vast research of Li
become increasingly popular. The working principles of such sys- intercalation into graphite, most of these systems use Liþ as the



tems have been compared to conventional cation-based rocking- cation, while PF



6 , BF4 , TFSI , F , ClO4 have been the popular an-
chair type batteries. Also, the chloroaluminate-based battery that ions [49]. In a dual ion battery, during charging, the cations inter-
involves an unusual electrolyte deposition reaction has been calate into the anode while the anions intercalate into the cathode,
discussed. simultaneously. During discharge, the ions deintercalate into the
electrolyte. The charge separation created by these simultaneous
intercalations can be seen as the mode of storage for such systems.
4.6.1. Aluminum ion/Chloroaluminate batteries
Such systems usually have higher operating voltages compared to
Aluminum, being a trivalent metal, can exchange three elec-
the respective cation only systems, usually above 4.5 V [49]. As
trons, thereby having a high theoretical capacity of 2980 mAh/g.
battery research has made progress over the years, dual-ion bat-
However, oftentimes Al3þ is not the active species in these batte-
teries have started employing charge transfer mechanisms beyond
ries. The high charge density of the trivalent Al3þ (54 pm ionic
graphite intercalation to alloying reactions as well. To move away
radius) compared to monovalent Liþ (76 pm ionic radius) results in
from Lithium, researchers have employed organic cations with PF
6
a high propensity of the ion to interact with the host lattices and
anions for dual-ion systems as well [50].
electrolytes. This makes the diffusion of the trivalent ion
complicated and often counter anions, such as Cl
form complexes
with Al3þ to form AlCl
4 which is also an intercalating ion. For
5. Best practice: reporting battery metrics
example, in the aluminum-graphite system, the following reactions
occur [40]; Although it seems obvious that battery metrics have to be
comparable between different laboratories and battery types, there
discharging is a surprising diversity of methods for obtaining these metrics. For
Cathode : Cn AlCl4 þ e
) * Cn þ AlCl

4
charging example, the specific capacity of an electrode is typically reported
discharging
in mAh/g. While current and time are unambiguous, the mass of
Anode : Al þ 7AlCl4
) * 4Al2 Cl

7 þ3e

the electrode has been published as a mass of active material, mass
charging
including additives (binder, conducting carbon), or other variations.
It is to be noted here that, unlike in conventional cation-based In this section, we will discuss key battery metrics and will suggest
batteries, the active ion being an anion results in graphite being the meaningful methods for reporting them.
cathodic species. The intercalation of AlCl
4 at graphite means that
Charge/discharge plots (curves) contain the key metrics for
only one e
can be exchanged, which nullifies the primary batteries. Fig. 5 shows the first three charges/discharge cycles of an
advantage of using trivalent aluminum species as active ions. aluminum-ion battery using a MoO3 cathode at a rate of 40 mA/g.
However, reports of reversible Al3þ intercalation in cathode ma- This example is typical, and we will use it to demonstrate the use of
terials, such as V2 O5 , TiO2 , and more recently, potassium-rich different battery metrics.
cryptomelane have been made, although competitive metrics have
not been achieved [41e45] (see Fig. 3). 5.1. Coulombic efficiency

4.6.2. Mixed-ion batteries The Coulombic efficiency, or charge/discharge efficiency, is the

The inefficacy of Naþ ion intercalation in common host mate- ratio of the charge extracted from the battery (Cd ) over the charge
rials, as well as the low degree of Naþ ion storage in most materials, injected to the battery (Cc ) over one cycle:
have prohibited the popularity of Naþ ion systems. However, in
Cd
2013, Liu et al. came up with the concept of using more than one h¼  100 (1)
Cc
active cation to circumvent the Naþ ion problem. They reported a
Liþ /Naþ mixed-ion electrolyte, which utilized a Naþ ion insertion/ Charge/discharge curves, as depicted in Fig. 5, record the time
extraction cathode and a Liþ ion extraction/insertion anode [46]. multiplied by the (usually constant) charging/discharging current
The working principle of this battery, as depicted in Fig. 4, differs ic=d [mA/g] on the x-axis. Given that current is defined as flow of
from the conventional rocking-chair mechanism, as two different electric charge per time, and the fact that the electrode mass does
cationic species are simultaneously active on opposing electrodes. not change (constant mass), the Coulombic efficiency h of a charge/
6 R. Borah et al. / Materials Today Advances 6 (2020) 100046

Fig. 3. Working principles of conventional cationic rocking chair batteries and the chloroaluminate battery.

Fig. 4. Working principles of mixed-ion and dual-ion batteries. Left: Mixed ion battery mechanism where one cationic species comes out of an electrode and a different cationic
species inserts in the counter electrode. Right: Dual ion battery mechanism where the cations and anions are pulled apart to opposite electrodes on charging, then fall back together
into the electrolyte on discharge.

discharge cycle can be simply calculated by dividing the specific cycles in the example of Fig. 5 can be calculated to 94.4%, 95.6%,
capacity at the end of the discharging time by the one at the end of respectively. This is a very typical example, where some energy is
the charging time. In the example above, Cc of the first cycle is 88.64 required in the first cycle to equilibrate the battery chemistry. Then,
mAh/g and Cd was found at 78.65 mAh/g. Thus, the Coulombic ef- h approaches 100% in the following cycles.
ficiency of this cycle can be calculated to h ¼ 88:7%.
It is worth noting that the software of most battery testers offers 5.2. Capacity
this option automatically. Also, since the Coulombic efficiency can
be directly measured, not requiring any assumptions by the In section 5.1, it has been discussed that the Coulombic effi-
researcher, it is a straightforward and unambiguous metric. ciency of a battery charging/discharging cycle can be calculated
Coulombic efficiency is a measure of how much charge can be unambiguously from the specific capacities at the end of each
recovered from a battery relative to how much was required to charge/discharge curve. However, the specific capacity, and other
charge it. In other words, it quantifies the amount of charge that derived metrics depend on the mass in the denominator. Unfor-
drives irreversible side reactions in a battery. Typically, h should be tunately, there are no clear guidelines on how to determine the
very close to 100%. The Coulombic efficiency of the second and third correct mass for this value.
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 7

batteries require one to five cycles in order to equilibrate the bat-

tery chemistry, the “initial” capacity should be recorded after these
equilibration cycles.
It has to be noted that the cycle life of a battery is heavily
dependent on the depth of discharge (the percentage of the bat-
tery's total capacity that is being used in one cycle). It is, therefore,
necessary to report not only the cycle life of a battery but the cycle
life at the respective depth of discharge. Realistically, a battery is
only used within its quasi-linear potential range. For the example in
Fig. 5 this means that a realistic depth of discharge would be
roughly at 40% (discharge until 25 mAh/g at a total capacity of 65
mAh/g for the second cycle). The capacity at the end of the quasi-
linear region is called maximum reversible capacity.

5.5. Energy density

Fig. 5. Typical battery charge/discharge curves. The example shows the first three The energy density of a battery describes how much energy the
cycles of an aluminum-ion battery using a MoO3 -based cathode and a charge/
device can store per mass or volume. Thus, the energy density can
discharge current of ic=d ¼ 40 mA/g.
be simply calculated by multiplying the specific capacity by the
voltage. If we use the second cycle of Fig. 5 as an example, the
From a user perspective, it would be useful to report the specific energy density of this battery would compute to
capacity relative to the mass of the whole device. This is what 1:3V  65mAh=g ¼ 84:5 mWh/g, indicated by the grey rectangle in
vendors and end-users should do. However, since the masses of the figure. Although this is the common way to calculate the energy
battery casings, current collectors, and other battery components density, it has to be noted that this is a very optimistic approxi-
can vary substantially without affecting the performance of the mation, given that the correct energy density equals the area under
battery, this would not be meaningful for research and develop- the discharge curve. Furthermore, as discussed above (sections 5.2
ment purposes. and 5.3), the electrode mass and battery voltage can be determined
On the other hand, typical electrode materials contain an active in different ways, which makes it imperative to report how these
material (for example graphite), as well as additives, such as con- values have been measured, if the energy density is being reported.
ducting carbon and binders. Reporting the mass of the active ma- For end-users, the useable capacity (or energy density) is much
terial would only be equally meaningless, since additives cannot be more relevant. This can be calculated by multiplying the specific
omitted in an actual device. Therefore, we recommend to base the capacity (energy density) by the depth of discharge or multiplying
specific capacity on the combined masses of anode or cathode the maximum reversible capacity by the voltage. In the example
materials, including additives. used here, the useable energy density is thus 33.8 Wh/kg.
The mass of the electrolyte should also be omitted in research
reports because the volume of electrolyte required depends on the 5.6. Factoring in cost
fabrication and configuration of the device.
Although this is not relevant for purely scientific work, the cost
of storing energy is of huge significance for end-users. A useful
5.3. Voltage
metric to factor in the cost of the materials is the cost of useable
capacity/energy. In scientific work, it is important to be able to
When discharging a battery, the voltage constantly changes and
directly compare the performance of the active materials them-
in a nonlinear fashion (cf. Fig. 5). However, the voltage is an
selves, as various research groups may use different additives.
important parameter that goes into derived metrics as outlined in
Therefore, the mass and cost units have to be based on the active
section 5.5. Unfortunately, there are different methods in the
materials of both cathode and anode, as well as the minimum
literature on how to determine the voltage, for example, by using
amount of electrolyte required. The cost of useable capacity/energy
the voltage where the charging and discharging curves intersect
can then be determined by dividing the cost of materials per unit
[51]. It can be easily seen in Fig. 5 that this method overestimates
mass by the useable capacity/energy. Including the performance
the voltage significantlydit would be at about 1.7 V in this example.
and cost characteristics based on the total electrode or cell is also an
In a typical battery, after an initial nonlinear potential drop, the
honest way to accurately assess the current economic viability of
discharge voltage enters a region where it decreases linearly. At the
the product.
end of this quasi-linear region, the voltage drops further, rapidly. In
practical applications, only the quasi-linear region is useful. Fig. 5
5.7. Power density
shows an example of a quasi-linear region. Following this logic,
the average of the quasi-linear region is a good estimate for the
The power density of a battery is the maximum power that a
battery voltage. In the above example, this voltage can be found at
battery can deliver based on its mass (W/kg in SI units). The power
approximately 1.3 V. More accurately, the voltages at the beginning
density depends on the kinetics of the charge migration and the
and the end of the quasi-linear region can be provided.
transfer of the device. For example, batteries, where faradaic pro-
cesses are involved, generally have a lower power density
5.4. Cycle life compared with supercapacitors, where charges are just trans-
ported. Similarly, systems involving bulky ions or highly viscous
The cycle life represents the number of times a battery can be electrolytes have lower power density than those featuring highly
charged and discharged over its lifetime. According to the industry mobile charge carriers. Power densities can be measured by cycling
standard, a battery has reached the end of its lifetime, when the the battery at different charging/discharging rates and then work-
(specific) capacity has reached 80% of its “initial” value. Since ing out the maximum power density of these experiments.
8 R. Borah et al. / Materials Today Advances 6 (2020) 100046

6. Promising electrode materials The intercalation of sodium into graphite can, however, be
achieved through intercalation of solvated ions [54e56]. By
6.1. Anodes chelating the cations with linear polyethers, such as diglyme (bis(2-
methoxyethyl) ether), stable complexes resistant to reduction can
The use of metallic anodes in ion batteries has been the subject be formed. While successful, this method greatly reduces the
of much research for a very good reason. In order to maximize both theoretical capacity of the cell. Instead of intercalating a single
specific and volumetric capacities, one must be able to pack the sodium ion, a large complex must now intercalate, which will take
atoms into as little space as possible. The most efficient way to pack up much more space and have much more mass.
metal atoms is as the pure metal solid, therefore, using the pure While not technically graphite, hard carbons have also received
solid as an electrode material will give the highest theoretical ca- extensive attention over the years. These materials are usually
pacity available. produced by pyrolyzing cellulose at high temperatures ( > 1000  C)
The reduction potential of the Mnþ /M reaction is also usually [57]. These gained most attention after their successful imple-
very high e.g. Liþ/Li ¼
3.04 V, Naþ/Na ¼
2.71 V. This not only mentation in sodium-ion batteries by Dahn and coworkers [58].
means that a lot of charges be stored per gram or per cm3, but the This work showed successful intercalation of sodium ions at a ca-
charges can also be stored at a high energy, leading to higher en- pacity on the order of 300 mAh/g. However, this capacity faded
ergy densities overall. quickly, limiting its commercial viability.
Unfortunately, the use of metallic anodes is fraught with diffi- However, not all graphite is created equal, and different types of
culty. While each metal has its own quirks, the problems mostly graphite have shown to have different levels of performance. For
stem from the surface of the metal being very reactive. The ad- example, Wang et al. [59], investigated many different forms of
vantages and disadvantages of some of the most common anodes graphite as a cathode in aluminum ion batteries. Kish graphite
are summarized below. flakes (a highly crystalline form of graphite made as a byproduct of
the steel industry), natural graphite flakes, highly oriented pyrolytic
6.1.1. Graphite graphite (HOPG), spherical graphite powder (potato-shaped
Graphite is perhaps one of the most successful and attractive graphite), as well as acetylene black, were all compared. See Fig. 7.
battery materials found to date. Not only is it a highly abundant Efforts to improve upon graphite have been made; however,
material, but it also helps to avoid dendrite formation and the high they have been met with limited success. For example, “graphite
reactivity of alkali metal anodes. Not to mention the fact that it is foam” is a material that has been investigated, both as a free-
naturally conductive is also a huge positive. Another advantage is standing electrode material [60], as well as a support onto which
that it is very easy to study material with many techniques, such as materials may be coated [61,62]. Graphite foam is produced by
Raman spectroscopy, X-ray diffraction, XPS, and more being uti- expanding the interlayer spacing of graphite, allowing for an
lized with relative ease. increased surface area while maintaining high conductivity
Graphite is not only the benchmark nonmetallic anode for throughout. The increased gap between the carbon layers can also
lithium systems, but it is also the benchmark cathode for conven- facilitate easier intercalation into the structure, as demonstrated by
tional aluminum ion batteries. The maximum stoichiometry ach- Wu et al. [60] and Lin et al. [52].
ieved for lithium is LiC6 giving a theoretical capacity of 372 mAh/g. Functionalizing graphite can also have an effect on performance.
For aluminum ion batteries, it is the AlCl-4 ion that intercalates [52]. In particular, graphite fluorides have been extensively studied for
However, the specific capacity in this system is much lower, usually lithium-ion and aluminum ion batteries [63e66]. The process of
between 60 and 70 mAh/g [18,25,40]. fluorination can increase the surface area of the graphite leading to
The general mechanism is also fairly simple. Ions intercalate into an increase in observed capacity [65]. Surface fluorination can also
the layers of carbon atoms, which expands the lattice. As the ions have an effect on the formation of the solid electrolyte interphase
deintercalate, the lattice relaxes back, thus making way for a highly [64].
reversible process [25,53]. Fig. 6 shows two different models for Battery research has not been immune to the “graphene boom”
intercalation. The Rüdorff model has ions intercalate fully along in recent years [67e72]. However, it is hard to imagine these sys-
layers one at a time, whereas the Daumas-He rold method shows tems making it to market any time soon.
partial intercalation in different layers in an ordered fashion before Overall, graphite represents a benchmark to which all other
both finish at the fully metalated “stage 1” complex. materials should be held to. Not only is it effective in terms of the
The formation of these graphite intercalation compounds (GICs) underlying electrochemistry, but it is also incredibly cheap and easy
is a charge transfer process where electrons are transferred into the to process. Being naturally conductive does not hurt either. This
graphite molecular orbitals giving the structure a negative charge. means that the active material does not need to be “diluted” with
This can then interact with the positively charged ion [28]. Inter- an extra conducting additive, such as “Ketjen Black” or “Super P”
estingly, in aluminum ion batteries, graphite is used as a cathode, conductive carbon when electrodes are prepared.
and so the same phenomena occur with active species of the
opposite charge. Instead of electrons being transferred into
graphite, giving it a negative charge, the electrons are stripped 6.1.2. Lithium metal
away, giving it a positive charge. This allows for the negative AlCl
4 Lithium metal, in particular, has caused many problems over the
ions to intercalate in the same way as conventional positive ions do years. The idea of using lithium metal in a cell was proposed and
when graphite is used as the anode [52]. demonstrated by Whittingham in the 1960s [73].
Interestingly, graphite has not found such widespread success in One of the most difficult aspects of using lithium metal to
either sodium or magnesium ion batteries despite the similarities navigate is the formation of dendrites on the surface upon plating
in size and or charge to lithium. In the efforts to explain this, a and stripping. Dendrite formation is a complex process, and many
quantum mechanical study was carried out by Liu et al. [32]. The theoretical models have been developed to try and describe the
results of this study showed that Na and Mg generally have the phenomenon and hopefully suppress it [74e77].
weakest binding for a given substrate arising from a competition In short, in standard electrolytes, lithium is deposited onto the
between the ionization potential of the metal ion and the ion- metallic surface in an asymmetrical fashion. Instead of plating
substrate coupling. evenly, the fresh lithium deposits as fractal spikes on the surface. If
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 9

Fig. 6. Two opposing mechanisms for the formation of graphite intercalation compounds. Upon removal of the ions, the scheme progresses in the backward direction. Reproduced
with permission from Ref. [53] Copyright 2014, Royal Society of Chemistry.

Fig. 7. A: Charge discharge curves for various types of graphite used in the study. Voltage plateaus all appear at roughly the same potential, but the capacity is vastly different. B: X-
ray diffraction studies of the different forms of graphite, this peak is related to the inter-layer spacing the structure. The colors in the legend represent identical materials throughout
both plots. Adapted with permission from Ref. [59] copyright 2017 American Chemical Society. Further permissions related to the material excerpted should be directed to the ACS.

these metallic dendrites grow large enough, they can puncture the 6.1.3. Sodium metal
separator and short the device [22,78]. Given that sodium sits below lithium in the periodic table, it is
As such, dendrite suppression is an active research area with substantially more reactive than lithium, which makes it difficult to
many different techniques being discovered; for example, coating work with. A fully developed battery using metallic sodium does
the anode with various materials, such as carbon nanospheres [79], exist in the form of Na/S batteries.
2-dimensional materials [80,81], or polymers [82] to form an arti- The Na/S system traditionally uses a solid beta-alumina elec-
ficial SEI. Alternatively, electrolyte additives, such as other lithium trolyte and operates at a temperature of between 300 and 350  C
salts or organic carbonates, have also been shown to suppress [83]. This is required for the movement of the active species
dendrite growth [19,21]. through this solid electrolyte, but also has the side-effect of keeping
While unlocking the true capability of lithium metal is a worthy the sodium anode in the molten state (Na m.p. ¼ 98  C). This, of
goal. The low relative abundance makes it unattractive in the long course, presents considerable safety concerns.
term. In the short and medium term, however, lithium will likely To date, little progress has been made in terms of a room tem-
continue to dominate the market. As a mature battery technology perature secondary battery using sodium metal. Work has been
that has excellent metrics, it will no doubt remain a benchmark for done on the plating and stripping of Na metal in organic electro-
many years to come. lytes, but molten salt systems are the main system used [84e87].
10 R. Borah et al. / Materials Today Advances 6 (2020) 100046

Cao et al. [88] have reported a functioning room temperature so- but the crucial difference with Mg is that the SEI layer is ionically
dium secondary battery by using 4 M sodium bis(fluorosulfonyl) insulating [89,95]. This means that once the SEI layer is formed on
imide in a variety of ether solvents. The sodium is initially plated the Mg surface, the battery is essentially dead as the charge cannot
onto a copper current collector and plated and stripped in subse- flow across the boundary. As a result, the majority of magnesium
quent cycles. battery research has focused on electrolytes that do not sponta-
The main aspect of working in sodium's favor is its natural neously decompose to form this SEI layer [89,91,94e99].
abundance compared to lithium. In all other aspects, sodium is left While initial systems focused on Grignard reagents, the field has
wanting. Its redox potential, while close, is not as low as lithium, settled on ethereal solvents, primarily tetrahydrofuran (THF), but
and its theoretical capacities are much lower owing to sodium's glymes have also been used more recently [99,100]. This SEI for-
much larger mass and size. mation also rules out a lot of commonly used salts, such as PF
6 or
ClO
4 as magnesium sources, which compounds the challenge
further [95].
6.1.4. Magnesium metal Work has gone into alternative anodes for magnesium ion bat-
One of the often stated advantages of magnesium metal batte- teries, but as always, the advantages of using the pure metal are
ries is that magnesium metal is “dendrite free,” unlike its alkali hard to ignore.
metal counterparts [89e91]. This is often attributed to the higher
rate of self-diffusion of the divalent metal on the surface. However,
recent work has shown this to be untrue (at least under certain 6.1.5. Aluminum metal
circumstances) [92,93]. Aluminum metal, while less prone to spontaneous combustion
In particular, Davidson et al. have shown, via calculations, that if than lithium or sodium, is still a highly reactive metal surface. In the
the rate of the electrochemical reactions (dictated by the charging air, this is quickly passivated to form aluminum oxide, which pre-
rate) is sufficiently high, one can expect dendritic growth to occur vents further corrosion and allows for easy handling and process-
[92]. Fig. 8 shows the results of these calculations. Regardless, ing. Similar to magnesium, this passivation layer is ionically
magnesium metal still has a large theoretical capacity (3833 mAh/ insulating. Likewise, much research has gone into the development
cm3 and 2205 mAh/g) and so getting it to work in a cell would be an of electrolytes that are able to break down the passivated surface to
admirable goal. perform electrochemistry with the reactive metal underneath
In spite of its seemingly dendrite free nature, magnesium metal [101].
is probably one of the most difficult battery materials to work with. Current literature on Al-ion batteries are biased toward a
Like all of the metal surfaces, it is highly reactive, and most elec- eutectic mix of AlCl3 and 1-ethyl-3-methylimidazolium chloride
trolytes spontaneously decompose on to form a “solid electrolyte ([EMIm]Cl). These studies represent about 2/3s of all academic
interphase” or SEI [94]. This is also observed in Li and Na systems, studies [18]. The chlorine from the [EMIm]Cl is more attracted

Fig. 8. A: Calculation comparing the rate of self-diffusion kd and the rate of reaction ke with the morphology of deposition. B: Kinetic Monte Carlo simulations for different current
density and diffusion barriers. C: A digital photograph of magnesium dendrites obtained during these experiments. Adapted with permission from Ref. [92] copyright 2019
American Chemical Society.
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 11

to the Lewis acidic AlCl3 , so an ionic liquid comprised of EMImþ and its crustal abundance, it sits well below lithium [16]. Silicon, on the
AlCl
4 ions are formed. Once the ratio of AlCl3 exceeds 1:1, Al2 Cl7


other hand, is the second most common element in the crust below
species are produced, which render the ionic liquid Lewis acidic, oxygen.
and it is then able to penetrate the oxide layer to the fresh, reactive
Al metal underneath.
However, this [EMIm]Cl-based electrolyte is expensive, which 6.2. Cathodes
severely limits the commercial potential, despite often being
coupled with a cheap graphite-based cathode. Also, current col- 6.2.1. Sulfur
lectors for the cathode are often based on expensive molybdenum Sulfur is one of the holy grails for battery materials. It is not only
or tungsten metal, so an overhaul of the electrolyte and current abundant, but it also boasts of a maximum theoretical capacity of
collector are needed for commercial viability. Currently, Al-graphite 1675 mAh/g (this assumes that each sulfur atom gains two elec-
batteries are limited to energy densities, similar to lead-acid [102]. trons during discharge). Compared to the standard LiCoO2 , which
So, if energy densities greater than lead-acid are desired, a cathode has a theoretical capacity of 274 mAh/g, although only half the
material with the ability to reversibly intercalate the highly charge lithium can be removed in practice, meaning that the capacity is
dense Al3þ is needed. limited to half that figure [30]. The electrochemical potential,
combined with sulfur currently being in oversupply [120], makes it
a very attractive option.
6.1.6. Alloying electrodes However, sulfur is not without issues. The three main problems
As stated, using the native metal as the anode material in a holding back sulfur are its low conductivity, the large volume
secondary battery is the benchmark anode in all cases. However, as expansion upon reduction, and the polysulfide “shuttling” phe-
outlined, the native metals often come with practical problems nomenon [30]. For amending the conductivity, the sulfur is often
stemming from their extreme reactivity. Using an anode capable of diluted with a conductive material like Ketjen Black, carbon
forming an alloy with the metal, for example, Na3Sn is another nanotubes, or other carbon-based conductive matrices in which the
alternative that often leads to high capacity systems. sulfur can sit [30,121e123]. This is a common practice for many
As mentioned in section 4.4, various metals have been investi- materials, but it is still an important consideration, especially in
gated for this purpose, but the most common across all ion systems light of the volume expansion issue. Upon complete reduction to
are Si, Sn, and Sb. The main issue for all of these metals is the large Li2S, the volume of the sulfur cathode is expected to increase by
volume expansion sustained upon metalation. For example, going more than 170% [30]. This places large mechanical strain on the
from Sn to Li4.4Sn shows a 260% volume change [103], going from cathode, which can result in cracks. This disrupts the connection
Sn to Na15Sn4 shows a 420% volume change [104]. The larger the between the conductive carbon and the sulfur, causing degradation
active ion, the greater the volume expansion. of performance.
This volume change causes the “pulverization” of the material, The final drawback of sulfur is the polysulfide shuttle effect.
which impacts the electrical contacts and causes the capacity to Sulfur as a material is made up of S8 rings that undergo sequential
fade rapidly [105e107]. This is shown in Fig. 9, where on the initial reduction to S2
. First, the ring is split, making S2
8 with a stoi-
charge, the material swells and cracks. An SEI is also formed at this chiometrically appropriate amount of the active ion. In the case of
stage. Upon discharge, the material shrinks, cracking even more. monovalent cations, one cation simply attaches at either end of the
This is exacerbated over many cycles. sulfide chain [30]. In the case of magnesium, on reduction a Mg2þ
Once the contact is broken, the ions become stuck in the lattice ion keeps the ring intact by the two end sulfides bonding with it to
and cannot flow out again. One novel solution to this problem by form MgS8 [124]. Next, the sulfur is progressively reduced, and the
Ryu et al. was to apply pressure to the cell, which pushed the chain shortens to S2
x (where 3  x < 8) are formed. It is these in-
particles closer together and restored electrical contact [108]. termediate species, which are often soluble in the electrolyte
More delicate methods have also been applied to try and solve [30,125]. The final step is further progressive reduction all the way
the volume expansion and its associated problems. The general to S2
. Fig. 10 illustrates the progressive reduction pathway of the
approach involves the formation of some form of composite, S8 ring. The lower order polysulfides where x < 3 tend to be insol-
whether it be intermetallic, for example, SnSb, Cu2 Sb [109e114], or uble in most conventional electrolytes [30,125]. Exactly which
carbon based [103,115e119]. polysulfides are soluble in the electrolyte will depend on the
Another aspect that is often explored along with these com- electrolyte used. How this progressive reduction mechanism works
posites is nanostructuring. These solutions do show promising re- in the case of the trivalent cations, such as Al3þ , is not fully known
sults; however, in terms of long-term application, caution must be and is not discussed in the literature as far as the authors can see.
taken. As previously mentioned, materials like carbon nanotubes However, there will have to be more than one sulfide chain
should be removed from consideration in terms of scale and quality involved in order to satisfy the stoichiometry.
of production. There are various methods to suppress polysulfide shuttling,
Out of these anodes, the only real long-term competitor appears which broadly fall under two strategies, namely, cathode engi-
to be silicon. Tin is often said to be a cheap material, but in terms of neering and electrolyte engineering. Cathode engineering generally

Fig. 9. Showing one of the main failure modes of electrode materials that undergo a large volume change. As the material is metalated, an SEI grows, and cracks appear in the
structure. Upon demetalation, the material shrinks and cracks, which affects performance greatly. Adapted with permission from Ref. [107] copyright 2107 Springer Nature.
12 R. Borah et al. / Materials Today Advances 6 (2020) 100046

are only known as primary cells, and so are beyond the scope of this
article. Like its group neighbor sulfur, the capacity of this anode is
extremely high; however, there are still many factors impacting the
performance of the cathode. In particular, the morphology of the
carbonaceous air-electrolyte interphace has a huge influence on the
end performance of the battery. As one might expect, the surface
area of the substrate is proportional to the true capacity of the cell
[136]. However, this is not the full story as for Li-air cells, pore size is
a more important factor [135] smaller pores can be clogged more
easily with the various lithium oxide precipitates that form during
discharge [135]. Increased structural complexity usually comes
hand in hand with increased cost, and so care must be taken to stick
to cheap and effective methods of obtaining the desired
morphology.
In the case of Zn-air batteries, an aqueous solution of 30% KOH is
used as the electrolyte. This serves many purposes. First, it signif-
icantly reduces the rate of hydrogen evolution at the Zn metal
surface [137]. Unfortunately, it is still not enough to make the re-
action nonspontaneous under these operating conditions (Zn/
ZnO ¼
1.26 V vs. SHE, H2O/H2 ¼
0.83 at pH 14). This concen-
tration of KOH also shows the greatest electrolyte conductivity
[138].
Perhaps the most promising, low cost, and environmentally
benign metal-air battery is Fe-air and FeeOH. Usually, metal-air
batteries show poor cycling efficiency. This limits commercial
viability due to energy being a relatively expensive component in
Fig. 10. Progressive reduction pathway of the S8 ring to S2
sulfide ion. Some inter-
the operating cost over the life of a battery. If energy is wasted, then
mediate steps omitted to keep the diagram succinct.
this cost component increases. Generally, Fe-air-based batteries
manage efficiencies of 55e70% [139,140]. However, Manohar et al.
involves the trapping of the polysulfides by providing a physical have shown that FeeOH batteries can have efficiencies as high as
barrier, which is still conductive to the active ions, or by anchoring 96% [139] with the use of carbonyl iron coated via electrodeposition
the polysulfides. The anchoring occurs through attractive forces, with bismuth sulfide. Carbonyl iron is a highly pure form of metal,
such as Coulombic attraction, with the addition of functional and this is a common anode in high-efficiency iron batteries [140].
groups. Some barriers include porous conductive carbon matrices Without Bi2S3, Manohar et al. achieved an efficiency of 89%, while
[126,127], core-shell structures [128] or alucone coating [129]. after the electrodeposition of Bi2S3, efficiency as high as 96% was
Anchoring can be achieved through sulfur-polyacrylonitrile achieved. The high efficiency is due to Bi2S3 forming elemental Bi
composite nanofibers [130], copper nanoparticles [131], or even on charging. This increases the overpotential for hydrogen evolu-
metal-organic frameworks (MOFs) that have coordinately unsatu- tion, effectively suppressing the unwanted phenomena. So,
rated metal sites (often abbreviated as CUMs) [132]. These CUMs although Fe-air batteries generally have a lower capacity than other
can provide sticky Lewis acidic sites for the polysulfides to adhere metal-air batteries (Manohar et al. achieved 300 mAh/g with their
to [133,134]. Alternatively, MOFs can be used as a precursor to cell), the extremely high abundance of iron, coupled with one of the
highly porous, conductive, carbonaceous structures after pyrolysis highest metal-air Coulombic efficiencies make it a great candidate
[131,133]. for further research and development. In fact, Manohar et al. esti-
Electrolyte engineering provides another pathway for the mated that at commercial volumes, their battery could reach costs
reduction of the shuttling phenomena. Using a solid, ionically as low as $3/kWh. This is a figure that is nearly two orders of
conductive electrolyte means that the polysulfide species do not magnitude below 2019 prices, which were about $187/kWh on
have a solvent to dissolve/disperse into. Other solutions involve the average [8].
use of additives, such as bis(4-nitrophenyl) carbonate. This has In general, metal-hydroxide batteries may be preferable to
been shown to precipitate out the polysulfide species in LieS cells, metal-air ones. Generally, metal-air batteries require the use of
largely eliminating the shuttling phenomena and allowing LieS expensive catalysts, which negates the benefit of cheap electrode
cells to retain over 700 mAh/g after 300 cycles [35]. and electrolyte materials [140,141].

6.2.3. Metal chalcogenides

6.2.2. Air cathodes Most “standard” battery cathodes fall into this category. Ranging
Cells are usually closed systems, where the active ions flow from from V2 O5 to MoSe2 many compounds have been tested over the
one end to the other. Metal-air batteries flip this idea on its head years in all the different types of batteries. This article will be
using oxygen (ideally from ambient air) as the cathode material. limiting the discussion to elements identified in the first principles
The oxygen is either reduced to superoxide O
2 and/or oxide O
2

chapter, namely Ti, V, Mn, and Fe and their oxides and sulfides. In
upon discharge and then oxygen O2 is regenerated upon charging. general, however, these materials possesses both a high redox
Oxygen is the single most abundant material that could be used as a potential, moderately high capacities, and fast, reversible reactions.
cathode; hence, if it could be paired with an abundant metal anode
in the earth, then it could turn out to be the cheapest cell chemistry 6.2.4. Titanium oxides
of all. Titanium dioxide is mostly known as a white pigment for paint
The most studied batteries of this type is the Zinc-air and Li-air or as an active layer for dye-sensitized solar cells [142]. However, it
battery. Other metals have been used, such as Mg and Al, but these has also found use as a battery material. Interestingly, titanium
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 13

oxides have been used primarily as anodes where most other mechanism, and at a bare minimum, X-ray diffraction studies must
transition metal chalcogenides act as cathodes. also be undertaken.
As with most materials, the bulk of the research is based on A similar result was observed for other transition metal oxides
lithium. The insertion voltage for TiO2 is higher than that of [34]. This means that in the future, as we move away from lithium-
graphite, ca. 1.5 V vs. Liþ/Li compared to 0.2 V vs Liþ/Li for graphite ion batteries, we may also have to move away from these materials.
[143]. While this does lower the voltage of the battery, it can avoid As previously discussed, some of these problems can be avoided
the formation of SEI layers, which usually form at lower voltages with nanostructured materials; however, in the long term, it may
[144,145]. be better to investigate other materials entirely.
The main advantage of the titanate spinels as anodes is the Beyond V2 O5 , VO2 has also gained attention recently as a
increased surface area compared to the traditional graphite. This potentially viable material [167]. The crystal structure of VO2 is
means that the possible charging and discharging rate is much shear-type, and so is more tolerant of ion insertion and removal
higher than traditional cells [146e148] As a result of the increased [168,169].
cycling capabilities, lithium titanate cells have found applications in Because transition metals are not naturally conductive, they
some electric vehicles, where having a high power density (W/kg) often need “diluting” with binders and conductive carbon
is just as important as having a high energy density (Wh/kg). when used as electrode materials. One way around this, as
The decreased voltage of lithium titanate cells does decrease the demonstrated by Dai et al. [170], where a composite material
energy density of the cells. A pleasant side-effect is that it makes of VO2 and reduced graphene oxide was made. This eliminated
them safer [149,150]. In traditional Li-metal or Li-graphite cells, the the need for a binder and also made the resulting zinc ion
lithium atoms are stored in the anode with a very high potential batteries flexible on top of allowing for fast charging. While
making them much more reactive with air or moisture. With a impressive, the use of reduced graphene oxide presents issues
lower potential anode, cell failure can be less catastrophic. of scalability.
The cycling performance of these cells is also improved
compared to other systems with cells in literature achieving 6.2.6. Transition metal sulfides
3000e7000 cycles [151e153]. As lithium becomes more and more One way to increase the mobility of charges within a lattice is to
expensive, cell lifetimes are going to play an ever more important use softer anions that can polarize more easily and allow passage of
role. intercalating species. Moving to transition metal sulfides accom-
Fast charging rates are becoming increasingly important in plishes this goal. Selenides and tellurides would have an even
battery technology as the push toward electric vehicles continues. greater effect, but these are excluded based on their abundance.
While clever engineering of a battery management system can While moving down a group does increase the polarizability of the
improve charge times, the underlying chemistry is a major factor, anion, it also increases the atomic mass of the anion, which means
and lithium titanate cells appear to have found their commercial that the theoretical capacity is generally lower for these materials
niche in this space. compared to their oxide counterparts. However, theoretical ca-
pacity is only part of the story.
6.2.5. Vanadium oxides While ion mobility in the sulfides may be higher, the voltage of
Vanadium oxides as a material have been used in all of the major these electrodes is also lower [171]. This leads to trade-offs in both
ion batteries at some point in their research history. It is generally a capacity and voltage, which greatly reduces the energy density of
cheap material, with vanadium(V) oxide being the cheapest. The batteries that use sulfides as cathode materials.
price generally increases with decreasing oxidation state, and as a The most commonly investigated transition metal sulfide is
result, this discussion will be mostly centered around V2 O5 . molybdenum disulfide MoS2. With its layered structure, similar to
On top of this, many attempts have been made to engineer a that of graphite, it has found a lot of success across a range of ion
large variety of nanostructures for this material ranging from batteries [172e175]. However, the low abundance of Mo makes it
nanoflowers to nanorods to xerogels [154e162]. As with most hard to consider for applications in the long term. Of the transi-
materials, lithium has found the most success with V2 O5 and due to tion metals identified as abundant enough to be useable in the
its small size and low charge, it is able to intercalate up to two Li- long term, titanium disulfide TiS2 is the most studied material
ions per V2 O5 unit reversibly [163,164]. A third Li can also be owing to it being the first lithium ion battery material. MnS2 VS2
intercalated, but this is not a reversible process due to a phase and FeS2 have also been used, but in a very limited fashion
change [163,164]. Orthorhombic V2 O5 is the most common poly- [70,176e180].
morph to use because of its structure. Titanium disulfide was the first cathode material used in
With the higher charge density ions Mg2þ and Al3þ , there is rechargeable Li-ion batteries by Whittingham [73]. It was chosen
little to no reversible insertion achieved [165]. This is due to strong for being both the lightest and the cheapest transition metal
interactions with the highly ionic lattice [157]. It is not purely a size available. Its layered structure allows for the reversible intercala-
effect as both of these ions have a smaller ionic radius than Liþ . tion of metal ions. However, it fell out of favor quickly due to its
Recently there has been some controversy with the V2 O5 in relatively low voltage and poor cycle life [176]. Due to it being a
magnesium ion batteries. It has been observed that using hydrated semi-metal, TiS2 has a high conductivity which may make it
V2 O5 increases the observed capacity of the cathode material. It attractive for solid state batteries [181].
was reasoned that the greater ability of the hydrated lattice to Transition metal chalcoginides have been the prototypical
“screen” the charge dense magnesium ions allowing them to flow cathodes for ion batteries for as long as ion batteries have existed.
more freely through the structure [155,166]. However, Lim et al. They have a crystalline structure, which can go through a phase
[165] showed through an extensive study that the reversible ca- transition to accommodate other ions and their redox reactions are
pacity stems mostly from proton insertion and while Mg2þ is easy to detect and understand. However, it is important to consider
inserted it is only to a very low degree Mg0.17HxV2O5 (0.66  x  the abundance of potential materials available when building
1.16). This work also disproved the hypothesis of the cointercalation economically viable systems.
of species, such as MgðH2 OÞ2þ y . This research also highlights the Caution must also be excised when choosing from the wide
need for high levels of proof for claims surrounding an intercalation variety of morphologies of these materials available. Nano-
mechanism. Electrochemical results are not enough to prove a architectures are an attractive solution to gain some extra
14 R. Borah et al. / Materials Today Advances 6 (2020) 100046

performance, although if the synthesis of complicated composites As with separators, development of current collector’s area is
is too difficult or time consuming, then it may not be an econom- relatively slow, but as shown above, this often overlooked
ically viable solution. component can be incredibly important in the quest toward the
maximum energy density. The use of better current collectors is
6.3. Other cell components tightly tied to the development of new electrolytes that are
compatible with cheaper metals.
While the most attention in battery research is paid to the active
materials and the electrolytes, a fully commercialized battery has 6.3.3. Binders
many more components than just those. Inside the cell, separators When preparing an electrode for use in a cell, the active material
and current collectors play crucial, yet often under-appreciated, is combined with some highly conductive carbon to increase the
roles. The material that encases the cell must also be considered conductivity and a binder to improve mechanical properties and
for cost and ease of use. increase adhesion to the current collector.
The binder is another often overlooked component of a battery,
6.3.1. Separators but on larger scales, it too will need to undergo closer scrutiny. The
Separators serve as a barrier between the anode and cathode, most common binders used are polyvinylidene fluoride (PVDF),
which prevents a short circuit. However, they must still be polyterafluroethylene (PTFE) or styrene-butadiene rubber (SBR)
permeable to allow the active species to flow between the elec- (the latter being used in conjunction with carboxymethyl cellulose
trodes. Since, in their most simple incarnation, they exist only as a (CMC))
spacer, it is most important that they are inert under operating The fluorinated polymers, in particular, potentially pose envi-
conditions. ronmental risks at the end of the cell's life [183,189]. CMC is a great
On the small/lab scale, glass microfiber is a common material, alternative that, as of right now, is mostly used in the production of
but for larger scale and commercial products, carbon based poly- anodes for lithium ion batteries but has also found use in other
mers, particularly polyolefins, are the standard. Commercial sys- systems [190e193].
tems also use separators as a fail-safe mechanism. If the Binder free electrodes have also occasionally appeared in the
temperatures get too high, the polymer melts, which stops the flow literature as an effort to produce a greener battery [194,195]. Some
of ions between the electrodes effectively shutting the battery of these systems, however, would be uneconomical in the long run.
down [182].
From a materials perspective, there is no current threat to the 6.3.4. Coating
supply of separator components. However, when separators Currently, the industry standard for the coating of the slurry
develop further to become thinner or allow for easier flow of the onto the current collector is by dispersing the dry mix of active
active species, it is important that this perspective is not lost. In material, binder, and conductive carbon into a solvent, commonly
particular, the environmental impact of functionalized polymers is N-Methyl-2-Pyrrolidone (NMP) [196]. This is a hazardous sub-
a concern [183]. There may also be a drive to use materials from stance, and it requires energy intensive drying, solvent recovery,
more eco-friendly sources, such as cellulose [184]. and purification systems, all of which require significant capital
expenditure. Moving away from toxic solvents toward benign sol-
6.3.2. Current collectors vents, or even dry electrode coating techniques can help reduce the
In a battery, the role of the current collector is to collect and cost and the environmental impact of the production of batteries.
deliver electrons from and to as close to the active material as Wood et al. compared water to NMP and found that using either
possible. It is usually a metallic substrate on which the active ma- solvent did not significantly change the contribution of cost to a
terial is attached. The main requirements for current collectors are battery pack (both being roughly 8e9%). However, using water as a
that they are conductive and stable/inactive under the operating solvent did reduce the post coating processing by saving two
conditions inside the cell. Current collectors are at least partially million dollars in capital expenditure [196].
exposed to the electrolyte, and so they must be carefully selected, Another popular technique that has started picking up the
or else they will corrode quickly [185]. traction of late is the dry electrode coating. The dry coating comes
In lithium ion systems, aluminum is commonly used as the with a myriad of benefits. It avoids the energy intensive drying
cathodic current collector. This cheap metal is readily passivated by process entirely, thus lowering capital cost requirements, is envi-
the PF-6 ion, which prevents further corrosion [186]. At the anode, ronmentally benign, and allows for comparable or even enhanced
however, the favored material is copper foil, which is far more performance compared to traditional coating techniques
costly. [197e200].
In standard aluminum ion systems, a corrosive ionic liquid
electrolyte is used. This means that conventional materials, such as 7. Electrolytes
stainless steel, copper, and nickel, cannot be used as they are
quickly corroded. On the lab scale, researchers have turned to much Electrolytes are a key research area that cannot be overstated in
more expensive metals, such as molybdenum or tungsten, to solve the development of effective batteries. An ideal battery electrolyte
this issue. An in-depth cost analysis by Munoz-torrero et al. showed must have the following attributes;
that in cells using these current collectors, they made up 53% and
70% of the cost of the final cell, respectively [187].  Electrochemical window: Electrolytes need to be stable over a
In the ideal case, some variants of steel would be suitable; wide voltage range that cell reactions can be accommodated
however, steel is often very susceptible to corrosion. Some research without electrolyte decomposition.
groups have attempted to use carbon-based current collectors;  Conductivity: High ionic conductivity and low electrical con-
however, to get the required conductivity, they have had to resort to ductivity is desired. A few mS/cm is the minimal ionic conduc-
using carbon nanotubes [188]. While these can impart interesting tivity considerable for battery electrolytes.
properties, such as flexibility to the cell, as previously discussed,  Viscosity: Electrolytes with low viscosity have higher ion
they are not suitable for large scale applications. mobility.
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 15

 Thermal stability: Thermally stable electrolytes, which are liquid Such safer solvents that can be produced via cost-effective path-
over a wide range of temperatures, are ideal. Solvents with high ways and that which leave a small environmental footprint are
flash points are safer. needed.
 Wettability: The electrolyte should also wet the electrodes and
the separator well so as to achieve consistent ion mobility. 7.2. Aqueous electrolytes
 Cost: Low cost and environmentally friendly electrolytes should
be preferred. Aqueous electrolytes have the potential to be far cheaper than
 Compatibility: Noncorrosive, nonreactive electrolytes ensure the their organic counterparts. However, there is a large trade-off when
longevity of cell components. considering the voltages that are able to be achieved. Theoretically,
at potentials above 1.23 V water begins to “split” into hydrogen and
Moreover, electrolyte design and composition should be care- oxygen gases. In practice, this electrochemical window can be
fully coordinated with the nature of the electrode surface. Altering extended by using electrode materials that sufficiently deactivate
the electrolyte can be one of the simplest ways to resolve problems the oxidation and reduction of water. For example, the lead-acid
associated with high energy electrodes. For example, the addition battery has an aqueous electrolyte that is able to operate up to 2 V
of fluoroethylene carbonate has been shown to limit dendritic since water electrolysis on the lead oxide electrodes is sufficiently
growth with the formation of a stable LiF solid electrolyte inter- slow and can be slowed further by the introduction of additives,
phase (SEI) layer on the Li anode [21]. Goodenough et al., have such as benzaldehyde [209,210].
shown the addition of bis(4-nitrophenyl) carbonate additive can In general, however, staying within the electrochemical window
precipitate out the troublesome polysulfide species in LieS cells, of water severely limits to operating voltage of cells to around 1 V.
almost entirely eliminating the shuttling phenomena and allowing For a system with identical capacity, this represents a four-fold
LieS cells to retain over 700 mAh/g after 300 cycles [35]. Adding an decrease in the energy density compared to traditional 4 V Li
extra chemical into an existing cheap, high-performance electro- based systems.
lyte is a low-cost mehtod to improve performance so long as the In spite of this, there is still a sizeable literature presence of
additives are not expensive or are only a small proportion of the aqueous batteries [211e216]. One of the major challenges for this
overall electrolyte. Common electrolytes can be classified as field is finding electrode materials compatible with water and
organic, aqueous, water in salt, ionic liquid, or solid. whose redox reactions occur within the limited electrochemical
window. For example, the intercalation of lithium into graphite
7.1. Organic electrolytes occurs at  -2.9 V vs. SHE. This is well below the thermodynamic
potential of hydrogen evolution (0.00 V vs. SHE), and so graphite
Organic electrolytes are the most well-known form of electro- cannot be used as electrode material in aqueous lithium-ion
lytes. These are what enable the batteries in our cellphones, laptops batteries.
and increasingly, vehicles. A typical organic electrolyte involves
dissolving a metal salt, which employs a large, and hence, weakly 7.3. Water in salt electrolytes
coordinating anion, such as BF


4 or PF6 to a standard 1 mol/dm
3

concentration. Typical ionic conductivities in organic solvents are Although organic electrolytes can provide excellent energy
around the 10 mS/cm mark [201]. Preference for organic solvents in densities due to their wide electrochemical window, there are
electrolytes can be attributed to their wide electrochemical win- safety concerns regarding their composition being made of flam-
dow compared to water. mable and toxic materials, which can limit their application [217].
Historically, organic carbonates, such as ethylene carbonate Aqueous electrolytes solve the flammability issue, but the electro-
(EC), propylene carbonate (PC), dimethyl carbonate (DMC), and chemical window is severely reduced, limiting energy density and
their mixtures have been used for Li-ion batteries. These solvents, commercial viability. Water in salt electrolytes benefits from wider
especially EC, are mandatory for 4 V operation of Li-ion batteries electrochemical windows than traditional aqueous electrolytes.
[202]. The passivation layer formed by EC and its high flash point, While aqueous electrolytes are limited by the splitting of water to
make it an essential component in carbonate solvent mixtures. 1.23 V, Suo et al. showed water in salt electrolytes can have elec-
However, carbonates cannot be utilized for high voltage ( > 5 V) trochemical windows as wide as 3 V [218]. This gives them the
systems, as this is beyond the limit of their anodic stability [203]. ability to facilitate the typical operation voltages of Li anode ma-
Various esters, ethers, and sulfones have also been used in Li bat- terials and produce high energy cells. Water in salt electrolytes is
teries [204e206]. Flamme et al. have reported a comprehensive defined by the mass and volume of the salt far exceeding that of
study on the selection of organic solvents for Li-ion batteries, in water. Suo et al.'s electrolyte was comprised of LiTFSI dissolved at
which they assess different solvents based on their physicochem- extremely high concentrations (molality > 20 m) in water. This
ical properties, as well as environmental impact and production results in all water molecules being a part of ion solvation shells,
pathways. They conclude that the introduction of nitrile and fluo- with no free water present. This is what allows for higher operating
rine groups can increase stability while alkoxy group insertions voltages compared to traditional aqueous electrolytes, which have
help reduce the melting point and increase conductivity. Also, copious amounts of free water present, and is, thus, limited to
general desymmetrization of solvent species increases solvation water's electrochemical window. However, this water in salt elec-
and decreases melting points [203]. The same classes of organic trolytes is inherently expensive. Li is a rare element, comprising
solvents have also been studied for other monovalent ion batteries, roughly 18 atoms in every million of the Earth's crust [16]. Most
such as Naþ , Kþ ion batteries [207,208]. organic electrolytes contain about 1 M of Li salt, so upscaling to tens
The biggest downside to these materials is their flammability. of times more Li is not a cost-effective method going forward. Not
Safety is a major consideration when commercializing a battery to mention the increased toxicity due to the increased concentra-
technology, and as advanced ion batteries become more and more tion of Li salts. LiTFSI is toxic upon contact or ingestion and can
ubiquitous, finding an electrolyte that is not inherently dangerous cause damage to organs. It is also corrosive to the skin and eyes
is of utmost importance. Noteworthy here are the solvents with [219]. One way Lukatskaya et al. circumvented these downfalls was
high flashpoints, such as Gamma-butyrolactone (95.5+C) and sul- to use the very water-soluble potassium acetate (KAc) in a mix with
folane (165+C), which can be safer alternatives to carbonates [203]. lithium acetate (LiAc). These are both benign and reduced the cost
16 R. Borah et al. / Materials Today Advances 6 (2020) 100046

of the electrolyte by an order of magnitude, all the while providing The requirements for a good solid electrolyte are much the same
the same extended voltage window [220]. Conductivity was also as for traditional liquid electrolytes; low cost, high safety, and
excellent, being as high as 31.4 mS/cm in the case of 27 m KAc, compatibility with electrode materials are all essential. However,
without LiAc. This is a much higher conductivity than traditional with solids, one must also consider the conductivity of the material.
organic electrolytes, which can achieve roughly 10 mS/cm at room Specifically, the solid electrolyte must be able to quickly conduct
temperature [201]. Water in salt electrolytes, therefore, shows great ions, but at the same time not be able to conduct electrons. While
promise in providing nonflammable, cost-competitive cells, these properties are somewhat inherent to liquid electrolytes,
particularly for applications where safety is paramount, such as in finding a solid that fits both of these properties can be challenging.
aviation. While many different materials fitting some of these categories
have been discovered. A full discussion of the field is outside of the
scope of this article, and so only the cheapest and abundant ma-
7.4. Ionic liquid electrolytes
terials will be covered.
If a material that has all of these properties is found then there
Ionic liquids (ILs) have a variety of both pros and cons. Due to
are significant advantages for these systems compared to tradi-
being a pure ionic mixture, they have a higher conductivity than
tional liquid-based electrolytes. Most importantly, they often allow
common organic electrolytes due to the sheer abundance of ions,
the use of metal anodes, which is highly desirable (see section 6.1).
similar to water in salt electrolytes. For example, a typical IL
Not only will the electrolyte not react with the metal and passivate
comprised of AlCl3 combined with 1-ethyl-3-methylimidazolium
the surface, as is common with liquid electrolytes, it will also
chloride (AlCl3 /[EMIm]Cl) in a 1.3:1 ratio achieves 20 mS/cm at
suppress the formation of dendrites, which is one of the main
room temperature [101]. Not quite as impressive as water in salt
reasons that metallic anodes are difficult to work with [22,74].
electrolytes, but still greater than their organic counterparts [201].
However, recently Li dendrites have been observed in a garnet-type
They also achieve a relatively large electrochemical stability win-
solid electrolyte by Ren et al. [226]. They found that the dendrites
dow of about 2.45 V in the case of the typical AlCl3 /[EMIm]Cl
were able to grow through to interconnected pores and short the
electrolyte [52]. There are less widely used ILs, which can achieve
cell. They suggest that these inorganic materials be kept as free of
much higher windows, such as 3.25 V in the case of aluminum
pores as possible to prevent this from occurring. Solid electrolytes
trifluoromethanesulfonate (sometimes called aluminum triflate)
fall into two main categories, inorganic and organic.
with 1-butyl-3-methylimidazolium trifluoromethanesulfonate
ðAlðOTfÞ3 =½BMImOTf Þ, or even as high as 5 V when using piper-
idinium-based salts [221,222]. IL electrolytes are most widely used
7.5.1. Inorganic solid electrolytes
in Al-ion batteries. Due to the need to break through the passivating
Inorganic solid electrolytes were the first to be investigated from
oxide layer, Lewis acidic electrolytes are needed.
both a fundamental and energy storage perspective. This is because
In order to make highly conductive, runny IL electrolytes,
the mechanism of ion conduction through inorganic solids is easier
awkwardly shaped cations, and anions are needed, where the
to understand and investigate. The possible mechanism for ion
overall charge is spread out over the molecule. These awkwardly
conduction has been explored in great detail. They range from the
shaped ions do not fit together easily, and thus, they have lower
vacancy mechanism, whereby the ions hop from one vacancy in the
melting points than highly regular salts with a comparable size
lattice to the next, or the interstitial mechanism, where the ions
between ions, such as NaCl (m.p. 801  C). Currently, in the Al-ion
hop from one interstitial site to the next [227].
literature, AlCl3 /[EMIm]Cl is the standard, representing about 2/3s
The most famous and successful inorganic solid electrolyte is b-
of all papers [18]. However, [EMIm]Cl, along with the other higher
alumina, a polymorph of Al2O3 with an unusual layered structure.
voltage alternatives are expensive, which severely limits commer-
In fact, a battery using this material was commercialized as early as
cial potential. As of September 2019, Sigma Aldrich stocks [EMIm]Cl
the 1960s. The high-temperature NaeS battery uses b-alumina as
at 98% purity for $87.30 USD/25g. Thankfully, there are ongoing
an electrolyte. A liquid electrolyte would not work in this particular
investigations into much cheaper alternatives, such as imidazole
instance because, due to the high operation temperature, both
hydrochloride, which Sigma stocks at $125.00 USD/500g. Xu et al.
anode and cathode material is molten [83]. This increased tem-
achieved an impressive 105 mAh/g after 1000 cycles at a high
perature also helps to increase the rate of diffusion of the ions
current density of 4 A/g using imidazole hydrochloride coupled
through the solid, which is advantageous.
with AlCl3 [223]. This is very impressive for a AlCl3 -graphite cell,
This system also reveals another major advantage of solid
where typically graphite achieves sub 100 mAh/g capacity [52,224].
electrolytes moving forward. Making a functioning metal-sulfur
More research into cheaper, high voltage window electrolytes is
battery is one of the main goals of the battery community at
needed if cheap, economically viable ILs are going to be commer-
large. However, there are several roadblocks hindering the
cialized for use in battery systems. Particularly, in the case where
development (see Section 6.2.1), in particular, the shuttling of
active ions have a highly negative reduction potential.
polysulfides resulting in irreversible capacity loss, as well as other
problems [35,225]. Polysulfides are generally too large to diffuse
7.5. Solid electrolytes easily through the lattice, and so this loss pathway is shut down.
Another important class of inorganic solid electrolytes is the
At first glance, the concept of a solid electrolyte seems strange. If Sodium Super Ion Conducting or NASICON type materials. These
the main role of an electrolyte is to facilitate the flow of ions be- generally take the form of AB2(PO4)3 formula where A is a mono-
tween the electrodes, then surely liquids would be the natural valent cation, Li, Na, or K and B is a metal ion generally Ti or Zr
choice. However, liquid electrolytes do have a few flaws. They can [228].
be unstable, both electrochemically and thermally, and they can be The main issue with inorganic electrolytes is the contact with
expensive and unsafe in many cases. The use of solid electrolytes the electrode [229,230]. Maintaining good contact is crucial for fast
can also aide in the use of high capacity materials, such as metallic charging and discharging, and if this contact is disrupted, then the
anodes and sulfur cathodes, by suppressing dendrite formation in cell is dead. This can be worsened further in situations where the
the case of the anodes, and polysulfide shuttling in the case of electrodes undergo large volume changes. The constant swelling
sulfur [225]. and shrinking of the material can break this contact [229,230].
 R. Borah et al. / Materials Today Advances 6 (2020) 100046 17

Because these materials are inherently not very flexible, there is not of electrolytes, such as solid electrolytes or with the addition of
much that can be done to improve this. additives in order to suppress unwanted behavior.
Less glamorous cell components, such as binders, current col-
7.5.2. Organic solid electrolytes lectors, and separators, should be continually assessed for eco-
The use of an organic material as an ion transport medium was nomic viability and environmental friendliness.
first demonstrated in 1973 by Fenton et al. [231]. It was shown that Lithium-ion batteries represent the vast majority of the current
poly(ethylene oxide) (PEO) was capable of chelating the ions, which market and research space; however, this boom cannot continue
can then hop from site to site and move along the chain [232]. indefinitely due to the rarity of lithium (and cobalt). A trend in the
Since then, many different polymers have been studied for this research space toward lithium-free battery alternatives can already
purpose. However, as usual, most of the research is done in respect be observed. Future research should focus increasingly more on
of Li-ion systems. Poly(acrylonitrile), poly(vinylidene fluoride) and these alternatives as a renewable economy will require a battery
poly(methyl methacrylate) have all been found as effective mate- market, which is much more diverse. For example, high-performing
rials although PEO still remains the most popular [233,234]. Poly- lithium-ion batteries will be used in areas where high energy
mers have the advantage of being easy to work with and above all density is required, whereas cheaper and more sustainable alter-
else, flexible. This feature opens up a wide range of possibilities for natives, such as sodium or aluminum-ion batteries, will be used in
improved design architectures and implementation in wearable areas where cost and scale are more important.
tech. This also solves the issues of inorganic solid electrolytes since
they are more able to accommodate volume changes in the active
Declaration of competing interest
materials.
Like the inorganic electrolytes, polymer electrolytes have to be
The authors declare that they have no known competing
used at an elevated temperature. Specifically, it must be above the
financial interests or personal relationships that could have
glass transition temperature for the polymer [232]. However,
appeared to influence the work reported in this paper.
polymers are much less thermally stable than inorganic materials,
such as b-alumina. They are also much more easily oxidized
compared to these materials, and so their operating voltage is References
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