Journal of Power Sources 395 (2018) 336–348

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Journal of Power Sources

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Review article

Sodium-ion batteries: New opportunities beyond energy storage by lithium T

a,∗ b
Ali Eftekhari , Dong-Won Kim
a
Belfast Academy, 2 Queens Road, Belfast, BT3 9FG, United Kingdom
b
Department of Chemical Engineering, Hanyang University, Seoul, 04763, Republic of Korea

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Sodium-ion batteries are reviewed

from an outlook of classic lithium-ion
batteries.
• Realistic comparisons are made
tween the counterparts (LIBs and
be-

NIBs).
• The challenges and potentials of NIBs
are subtly highlighted.
• NIBs need a subtle strategy of research
and a pragmatic roadmap.

A R T I C LE I N FO A B S T R A C T

Keywords: Sodium has been recently attracted considerable attention as a promising charge carrier, but this sudden at-
Sodium-ion battery tention has made the strategy of research somewhat hazy, as most research reports are indeed the examination of
Lithium-ion battery typical materials rather than following a solid roadmap for developing practical cells. Although the history of
Specific energy sodium-ion batteries (NIBs) is as old as that of lithium-ion batteries (LIBs), the potential of NIB had been ne-
Energy density
glected for decades until recently. Most of the current electrode materials of NIBs have been previously examined
Energy efficiency
in LIBs. Therefore, a better connection of these two sister energy storage systems can shed light on the possi-
bilities for the pragmatic design of NIBs. The first step is to realise the fundamental differences between the
kinetics and thermodynamics of Na as compared with those of Li. In fact, tiny differences between the elec-
trochemical behaviours of these systems can lead us to new practical ideas for designing suitable materials.
Furthermore, NIBs should be considered as new opportunities for energy storage rather than replacing LIBs.
Hence, the subtle strategy of research is to learn from LIBs but not replicate them when designing NIBs.

1. Objective
1.1. Historical background
The history of sodium-ion batteries (NIBs) backs to the early days of
lithium-ion batteries (LIBs) before commercial consideration of LIB, but
sodium charge carrier lost the competition to its lithium rival because
of better choices of intercalation materials for Li. During the 1960s,
various electrochemical reactions were utilised for designing batteries,
but most of these ideas did not survive for more than a few years. The
idea of LIBs in that era has been well reviewed by Scrosati [1] and
Jasinski [2]. The same strategy was also followed in the 1970s, but
some ideas became the centre of attention. For instance, metal-sulphur
batteries were subject of numerous investigations. At the preliminary
stage, the key requirement was to design a working system rather than
maximising the specific energy by a lightweight charge carrier.
Therefore, the focus was on sodium-sulphur battery [3] rather than the
lithium-sulphur counterpart.
In the late 1970s, the boundary of solid state science and electro-
chemistry was indeed a hot topic due to the growing interest in ionic

∗
Corresponding author.
E-mail address: eftekhari@elchem.org (A. Eftekhari).

https://doi.org/10.1016/j.jpowsour.2018.05.089
Received 21 March 2018; Received in revised form 24 May 2018; Accepted 29 May 2018
0378-7753/ © 2018 Elsevier B.V. All rights reserved.
A. Eftekhari, D.-W. Kim
conductance in solid structures [4]. Thanks to the massive advancement
in electrochemical instrumentation at that time, electrochemical in-
sertion/extraction of ions could be carefully monitored to understand
the mass transport within solids. Reversible insertion/extraction of Li
and Na into/from transition metal dichalcogenides provided the basis
for a new generation of rechargeable batteries [5–7]. Although this
family of electroactive materials and even heavier members are still
among the most common energy materials [8,9], the actual movement
was made by the possibility of intercalation/deintercalation into/from
layered metal oxides such as LiCoO2 and NaCoO2 [10]. It should be kept
in mind that this merely represents the general trend, and the history of
LIB is not straightforward. For instance, Campanella and Pistoia had
reported the electrochemical intercalation of Li into/from MoO3 in a
non-aqueous electrolyte back in 1971 [11]. Earlier works employing a
series of metal oxides have been reviewed by Jasinski [2,12]. However,
the concept of intercalation/deintercalation was not a central area of
research.
In any case, until the mid-1980s, the intercalation of alkali metals
into new materials was an active subject of research considering both Li
and Na somehow equally [5,13]. Then, the electrode materials showed
practical potential, and the focus was shifted to the energy storage
feature rather than a fundamental understanding of the intercalation
phenomena. At this stage, due to better electrochemical performance of
Li intercalation, Na became less attractive. Although Li could provide a
higher specific capacity, the main motive for inclining towards Li was
the excellent performance of electrode materials such as graphite anode
and LiCoO2. Introducing the commercial prototype of LIB in 1991 by
Sony was the last nail in the coffin of NIB. Since then, studies of NIB was
a marginal area of research along with LIB. Despite the limited natural
resources of lithium, there was no considerable scarcity in supply be-
cause the rapidly growing demand for LIB was limited to small portable
devices. Nevertheless, the market demand for battery-powered electric
vehicles provided an opportunity for the rebirth of NIBs.
There is now a tendency to catch up with LIB despite the lost history
of NIB. The number of research publications on NIB may surpass that of
LIB within a few years. This sudden attention can pave the path for the
birth of new opportunities for the next generation of NIB (or more
precisely, the first generation), but in the absence of a solid strategy of
research, it is not easy to draw a roadmap. In the case of LIB, the central
materials, graphite anode and LiCoO2 cathode, were known from the
early days, and the research strategies were to improve them or find
alternatives. This is hardly the case for NIBs, as there is still no such
central materials with satisfactory performance. Owing to the popu-
larity of this area of research, numerous reviews have been recently
published [14–28]. Most of these reviews provide a comprehensive
overview of various materials, which have been examined for NIBs.
The present paper attempts to adopt a different strategy to provide
an overall picture of the field. Instead of reviewing all available ma-
terials, the focus is on a selective collection from a conceptual per-
spective. These materials are compared with the Li counterparts to
build a better outlook on the NIB status and potential. Many research
papers consider both LIB and NIB together, but the purpose is usually to
show the applicability of the material under consideration for both
systems rather than a comparative study of the mechanistic differences.
Furthermore, the distinguishable differences in energy efficiency,
which is of both fundamental and practical importance [29], are
highlighted throughout the paper.
1.2. Li vs Na: a realistic comparison
Owing to the rapidly growing interest in NIBs, it is common in the
literature to compare NIBs with the available LIBs to highlight the ad-
vantages and disadvantages of NIBs. However, most of the statements
are unrealistic and do not lead us very far. Therefore, it is of vital im-
portance to clarify a realistic outlook for the future of NIBs. The key
point is that a cell is composed of various components whose weights
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Journal of Power Sources 395 (2018) 336–348
and volumes are constant regardless of the charge carrier. Since the
strategy of battery research is always practical to some extent, the
theoretical values for capacity/energy should be 'ideally achievable'
rather than superficial ones. A recent paper has quantitatively com-
pared the maximum achievable values for various Li batteries and their
counterparts [30].
When comparing LIB and NIB, two full cells should be compared. In
the current cell architecture, only 2.5% of a LIB is made of the charge
carrier, and the reset is the electrode materials, electrolyte, separators,
current collectors, etc. Albeit, an excess amount of the charge carrier is
required in the electrolyte, but the cell technology attempts to minimise
it as it has been the case since the early LIBs. Since this is a theoretical
comparison, we do not need to consider the availability of materials,
and we can assume that graphite can accommodate Na to the same level
of Li to reach the composition of NaC6 and the NaCoO2 can be charged
to Na0.5CoO2 (or even assuming Na0.5Li0.5CoO2 as the cathode mate-
rial). In this case, the same amount of materials can be placed within
the same volume since the volume of the Li and Na cells described
above are almost the same (the densities of LiCoO2 and NaCoO2 are 4.9
and 5.0 g cm−3, respectively). Therefore, the difference in the energy
densities of the LIB and NIB is proportional to their operating voltage
(i.e., only 10% higher for LIB), and thus, the theoretical energy density
of a NIB is only 10% lower than that of its Li counterpart. Note the
terminology, when referring to NIB, the B stands for 'battery', which
means at least a full cell.
It is often stated, even in the papers devoted to NIBs, that NIBs suffer
from a low specific capacity as compared with LIBs. The comparison is
indeed the theoretical capacities of metallic Li and Na anodes, though
the available LIBs do not operate based on a metallic Li anode. The
specific capacity of the anode has a minor impact on the overall specific
capacity of the whole cell [30]. Theoretically, 1 mol of the charge
carrier (7 g Li or 23 g Na) is required for 6 mol of carbon + 2 mol of
Li0.5CoO2 (i.e., 260.86 g of the active materials). As mentioned above,
we can ideally assume that the discharged cathode materials are
Li0.5Li0.5CoO2 and Na0.5Li0.5CoO2 for LIB and NIB, respectively. Hence,
if calculating the specific capacity with respect to the weight of
anode + cathode, the specific capacity of a NIB is only 10% lower than
that of a LIB.
Considering 0.2 V lower cell voltage of a NIB as compared with a
LIB, the overall theoretical specific energy is 279 Wh kg−1 and 231 Wh
kg−1 for a LIB and a NIB [30]. Evidently, the target theoretical specific
energy of NIB is only 18% lower than its LIB counterpart. Note that we
did not even consider the weight of the electrolyte, outer shell, elec-
tronic components, additives, etc., which are constant weights regard-
less of the choice of charge carrier. Albeit, these are all theoretical
consideration based on the constant weight of other components in
accordance with the available 18650 LIBs. There are also possibilities
for changing the cell architecture in favour of the specific energy, but
these improvements can be made for either LIB or NIB, and there is no
direct advantage for the lightweight charge carrier.
Theoretically, about 2% improvement in the specific energy is
possible because of the opportunity of replacing the anode Cu current
collector with a lightweight Al current collector in NIBs. This replace-
ment also has a considerable impact on the cost too, as will be discussed
in the next section.
1.3. Cost incentives
Despite the usual abundance of lighter elements, the natural re-
sources for lithium are 1/1000 less than those of sodium. This has been
initially considered as the prime motive for the development of NIBs, as
it is still frequently repeated in the literature. For instance, a brief note
calling lithium the new gold is among the highly cited papers of the
field [31]. It is true that sodium is cheaper than lithium, but the cost of
the charge carrier has a minor impact on the overall cost of a battery
since the other components are more expensive, and a significant cost
A. Eftekhari, D.-W. Kim Journal of Power Sources 395 (2018) 336–348

Fig. 1. The model systems are 7 kW, 11.5 kWh batteries. All costs are in US$. (a) Calculated cell material costs for the reference LiMn2O4 (LMO)–sG battery and a
theoretical LMO–sG battery in which the copper foil is replaced with aluminium foil and lithium is replaced with sodium. The diagonal lines indicate that there is a
change in the cost of a component between the two systems. (b) Cost breakdown of the cell materials for six modelled sodium-ion and lithium-ion batteries. (c) The
total cost, volume and mass for the six modelled batteries in panel b. Reproduced with permission from Ref. [32]. Copyright 2018, Nature Publishing Group.

goes for the manufacturing process. Therefore, if preparing similar LIBs
and NIBs, the final costs will be similar, and there is no significant
advantage for the NIB. In other words, the cost advantage of NIB has
been somehow exaggerated in the literature.
Passerini and his coworkers have recently made an extensive cost
comparison of LIBs and NIBs [32] as outlined in Fig. 1. Such studies can
shed light on the ambiguity of the research motives [33], by comparing
the cost of various components in NIB and LIB. If utilising similar ma-
terials, the cathode cost is only 3.6% lower in the case of Na as opposed
to Li. Considering the higher specific energy of LIB, still, LIB is cheaper
with respect to the unit of energy stored (both volume and mass).
However, a cost-effective advantage of NIBs is that the Cu current
collector of LIBs can be replaced with a cheap and lightweight Al cur-
rent collector. Since Al is not alloyed with Na, the Al current collector
can be used for both anode and cathode sides. This can reduce the cost
by about 8% [33]. On the other hand, the density of Al is less than 1/3
of Cu, and thus, the specific energy can be increased, in addition to the
discussion made above. It should be kept in mind that this is not a direct
advantage from the manufacturing perspective since the current cell
technology of LIBs should be altered. The price of LIBs has been
dropped dramatically during the last few years merely because of the
advancement in the cell technology. Replacing the Cu current collector
of the anode with an Al current collector is simple at the lab scale, but it
needs profound investigations for commercial manufacturing through
the same current collector is already employed on the cathode side.
Returning to the discussion made in Section 1.2, the specific capa-
city of a NIB can be substantially increased by replacing the Cu current
collector. Therefore, this advantage further contributes to the specific
capacity of NIBs to close the gap between two counterparts. In con-
clusion, the specific energy is not an issue of NIBs in comparison with
the Li counterparts. The current problem is the lack of appropriate
material as analogues to the available lightweight materials of LIBs.
1.4. Lithium scarcity: a real motive?
In reply to the arguments made in Section 1.3, one may raise two
points, as it is frequently repeated in the literature: the cost of lithium is
rising and we may run out of lithium. In fact, the sudden increase in the
lithium price during 2015/2016 ignited these concerns, which have
been reflected in the battery literature too [34]. However, these con-
cerns are based on two misconceptions, which have not been ade-
quately clarified in the battery literature.
First, contrary to what is frequently repeated, the price of lithium
was not tripled during the last 2–3 years, it was the price of battery
grade lithium carbonate. In other words, it was an issue of manu-
facturing battery compounds rather than a shortage in the supply of

338
A. Eftekhari, D.-W. Kim
lithium. Furthermore, recent market research suggested that the price
of lithium will drop by 45% until 2021 [35]. In fact, the price hike was
the result of an unpredicted demand, but the industry will soon adjust
the supply to meet the rising demand. It was indeed because of an
unusual synchronisation of various factors such as environmental reg-
ulations for reducing CO2 emission, governmental policies for shifting
to electric vehicles, the market success of electric vehicles and new
automakers such as Tesla Motors. Notwithstanding, it is unlikely to
witness such 'unpredicted' rise in the demand again.
Second, the natural resources of lithium are way higher than what is
usually considered as the limit of supply [36]. During the last 10 years,
the estimation of the lithium resources by the US Geographical Surveys
was increased by over 300%. On the other hand, the increasing demand
will justify exploitation of new resources [37]. Most discussions about
the lithium resources are limited to the easy-to-exploit brane resources
located in the so-called lithium triangle in South America. Even in the
latter case, Bolivia with the largest resources of three countries (Bolivia,
Chile, Argentina) has not yet started to exploit lithium (at a consider-
able scale) [38].
1.5. Motives and strategy of research
As discussed in Sections 1.3 and 1.4, the motives for developing
NIBs is neither cost nor scarcity of lithium. Although they have a po-
sitive impact, they are not sufficient motives for the development of
NIBs since LIBs can fairly meet the growing demand. LIBs have a rich
history of research, which is the prime advantage for the current
technological development and a disadvantage from the innovation
perspective. It is unlikely (or more precisely, very slow) to find new
opportunities in LIBs.
NIB has its own domain of research, which can provide a broad
range of new possibilities. The common mistake is to treat NIB as a
replacement to LIB. Therefore, as it will be reviewed in the present
paper, the successful cases of LIBs are usually adopted for the devel-
opment of NIBs. Nonetheless, NIBs can be developed based on mate-
rials, which are not considered in LIBs. For instance, Prussian blue and
its analogues were among the most common electroactive materials in
the 1970s era of solid-state electrochemistry [39]. Li was soon elimi-
nated from the corresponding research due to the poor electrochemical
performance of Li insertion/extraction. Na could be inserted/extracted
into/from Prussian blue for tens of thousands of cycles [40], the cy-
clability which is very uncommon for any Li system. This is the reason
that Prussian blue and its analogues are among the common candidates
for NIBs, but this is still an old idea. What the NIB development needs
are new ideas.
The strategy of research is not very progressive. A majority of works
are devoted to the composition of electrode materials for improving the
electrochemical performance of common electrode materials. At this
stage, most of the available candidates cannot provide satisfactory
performance for the practical development. Hence, it is useless to im-
prove them slightly. Instead, the current focus should be on the fun-
damental understanding of the solid-state electrochemistry of Na in-
tercalation to subtly design the electrode materials. In fact, the current
quest is for finding or engineering electroactive materials rather than
improving them. In this regard, we should learn from the Li systems but
not copy them, since they are substantially different, as will be dis-
cussed in the following sections.
In the case of sulphur batteries, as mentioned above, the history of
Na−S was even richer. When considering emerging batteries such as
selenium batteries [41], there is no historical advantage of Li−Se
battery over Na−Se battery, but still, the tendency is towards the
Li−Se battery. This is mostly due to the prospect of LIBs rather than
technical reasons. Therefore, Na batteries should be explored within
their own domains rather than replacements of Li counterparts, as there
is still no solid ground to justify this replacement.
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Journal of Power Sources 395 (2018) 336–348
2. General trends in the choice of materials
The current materials of NIBs are almost the same range of mate-
rials, which have been investigated during the past four decades in LIBs.
Kim et al. made a statistical analysis of publications during the past
years [42]. They showed that the majority of works on cathode mate-
rials are limited to layered metal oxides and polyanionic compounds,
while Prussian blue and its analogues are marginally studied. On the
anode side, the focus is on carbon materials and metal oxides, while the
marginal attention is paid to Na alloys. Owing to the success of inter-
calation materials with rigid lattice structure in LIBs, less attention was
paid to organic host materials. However, further attention is being paid
to the Na counterparts in the absence of ideal intercalation choices. Xu
et al. have recently reviewed the organic materials for NIBs in great
detail [43].
Owing to the popularity of nanostructures, there is a tendency for
preparing the electroactive materials in various nanostructured forms.
The advantage in battery systems is a shorter solid-state diffusion
length, which can be accompanied by a faster charging/discharging.
However, increasing the specific surface area increases the interfacial
problems, which might be more disadvantageous. On the other hand, a
higher surface area results in the possibilities of structural irregularities,
which can broaden the redox potential. The latter phenomenon is in-
deed the deviation form battery performance to pseudocapacitive be-
haviour [44]. There are several other disadvantages of nanomaterials
for energy storage applications such as low tap density. Hence, nanos-
tructured materials could not find a dominant role in the design of
battery materials.
However, nanomaterials can provide an extra advantage in the case
of NIBs. Since Na ions are larger than Li ions, the intercalation of Na
into small lattice structures (which are desirable for high-energy bat-
teries) might be accompanied by structural and volume change.
Utilising nanostructured architecture provides space to accommodate
the expanding volume [45]. Fig. 2 illustrates typical roles of the na-
noporosity for accommodating the large intercalating Na ions. This
strategy has been used to place the electroactive materials over a na-
nostructured scaffold where space is supplied [46–48].
3. Anode materials
One of the key challenges of NIBs is the anode material. For almost
three decades, the dominated anode material in the commercial LIBs
has been graphite. Although potassium-ion batteries (KIBs) can employ
graphite anodes, intercalation of Na into graphite is thermodynamically
unfavourable [49]. Despite the unsuitability of graphite for NIBs, gra-
phite is too enticing to be totally eliminated. Therefore, numerous
works have done to alter the solid-state electrochemistry of graphite for
the Na intercalation. The most promising approach is to co-intercalate
the solvent to make the Na intercalation possible [33,50]. Despite the
excellent electrochemical performance, this approach has two major
issues: (i) the co-intercalation can be conducted in an ether-based
electrolyte. This means losing the key advantages of carbonate-based
electrolytes, which have been the dominated electrolyte of LIBs since
the commercialisation. (ii) The co-intercalation of another species
means that half of the graphite capacity cannot be exploited for the
energy storage purpose, as the intercalated ether is not a charge carrier
(Fig. 3). There is no major difference between the capacity attained by
Li or Na intercalation. An interesting feature is that the electrochemical
performance of Na is better than Li in terms of energy efficiency [29], as
the hysteresis between the charge and discharge profiles is much
smaller for Na intercalation. This means lower overpotentials are re-
quired for the intercalation/de-intercalation of Na as compared with
that of Li. Nonetheless, the current status of graphite anodes does not
satisfy the practical requirements.
A. Eftekhari, D.-W. Kim
Fig. 2. Illustration of the reaction mechanism during initial sodiation and subsequent cycles. (a) Sodium-storage mechanism of CaV4O9, and (b) Sodium-storage
mechanism of VO2. Reproduced with permission from Ref. [45]. Copyright 2017, Nature Publishing Group.
3.1. Hard carbon
Hard carbon (HC) is among the most promising anode materials for
NIBs [51–53], but it has rarely been investigated for LIBs since graphite
anode perfectly works for the latter. Therefore, our knowledge about
intercalation into HC does not have a long history, and recent reports
have exhibited the practical potentials. Albeit, HC has also been tested
as a potential anode material in LIB, but there are a limited number of
works [54] including those using HC as a conducting agent for the
cathode [55]. Various HC samples have been prepared from different
natural products, and thus, it is not easy to compare the results reported
in the literature. In almost all cases, the carbonisation temperature has
an enormous impact on the electrochemical performance of the re-
sulting HC, but the common value of the optimum temperature is
around 1400–1500 °C [56,57]. In a recent paper, Ji et al. showed that
the rate capability of HC had been underestimated in the literature
[58]. The reason is the high overpotential of the counter sodium elec-
trode in a three-electrode cell. Therefore, when utilising an HC anode in
a full cell, the rate capability is much higher than the fundamental
studies. This suggests that the practical potential of HC anodes might be
more than what already reported in the literature.
3.2. Metallic sodium
Utilising the charge carrier as a metallic anode is beneficial in terms
of energy density as the maximum cell voltage and minimum anode size
can be achieved. However, since the commercialisation of LIB, metallic
Li anode has never been considered as a potential anode (though there
were some early commercial LIBs employing Li anodes) due to the
safety issues. However, recent advancements have provided an oppor-
tunity for reconsidering the metallic Li anode [59,60]. This possibility is
weaker in the case of NIB because the chemical reactivity of Na is
higher and the safety concern is more severe. However, this has not
fully eliminated this anode from the NIB research.
An interesting form of metallic Ni anode is the so-called anode-free
cell in which Na can be reversibly plated/stripped onto/from the Al
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Journal of Power Sources 395 (2018) 336–348
current collector [57,61]. As quoted above, a noticeable advantage of
NIBs is the possibility of utilising an Al current collector for the anode.
In the latter design, no anode material is used, and the charge carrier
after deintercalation of the cathode during charging is electroplated on
the current collector. This cell structure is theoretically the ultimate
design for the anode since the anode capacity cannot be enhanced any
further. However, the system is too complicated with various new
considerations, which should be taken into account such as the possi-
bility of dendrite formation, anomaly of the electrode/electrolyte in-
terface, etc. On the other hand, the presence of metallic Na in the
charged state can cause the same safety concerns due to its chemical
reactivity. For instance, the battery damage at the charged state can
easily cause an explosion as a result of contact with water or moisture.
3.3. Titanate spinel
Although having a relatively high potential vs Li/Li+, Li4Ti5O12 is
among the promising candidates of anode materials due to its excellent
performance. This anode material delivers a close-to-perfect flat pla-
teau, which is of great importance for delivering a constant voltage in
the full cell [62]. Following numerous investigations of Li4Ti5O12 in LIB
system, it has also been successfully employed for Na intercalation/
deintercalation. Owing to the larger size of Na ions, the electrochemical
performance is no longer ideal. A considerable behaviour is that the
overall anode potential is slightly lower for the Na intercalation system
[63–65]. The latter feature is of utmost importance as elevated the cell
voltage, which can close the gap between the operating voltages of LIB
and NIB. This is directly in favour of the energy density discussed
above. However, the cyclability is significantly poorer for the Na in-
tercalation while a noticeably lower capacity is achieved [65]. The
latter issue is not due to the weight of Na but anomalous intercalation,
which causes a deviation from the characteristic ideal battery perfor-
mance of Li4Ti5O12.
This difference between Li and Na intercalations occurs for almost
all metal oxide anode materials [66]. In other words, this phenomenon
is associated with the intercalation of larger Na ions within the compact
A. Eftekhari, D.-W. Kim
Fig. 3. Charge/discharge performance of a graphite anode in (a) 1 mM PF6 in
EC/DMC, and (b,c) 1 mM OTf in diglyme. Note that the redox activity of the
cells is given versus Li/Li+ and Na/Na+, Reproduced with permission from Ref.
[50]. Copyright 2014, Wiley-VCH.
lattice of metal oxides. As will be described later for spacious lattice
structures such as those of transition metal hexacyanoferrates, the Na
intercalation is more favourable. In fact, a design of the appropriate
intercalation materials for NIBs requires appropriate diffusion channels,
which are substantially different from those of counterpart Li-based
materials.
3.4. Conversion materials
Conversion-based electrode materials are usually in the elemental
forms or simple compounds since the electrochemical reaction is based
on low oxidation states. Therefore, almost all conversion-based mate-
rials are targeted for anodes due to their low redox potentials. Contrary
341
Journal of Power Sources 395 (2018) 336–348
to the intercalation metals in which there is a rigid lattice structure
made of various elements, convention materials are composed of ele-
mental structures (or compounds which can be separated to elements).
In this case, there is no solid architecture for accommodating the
coming ions. Instead, a larger structure is formed with the charge car-
rier. Obviously, this process is accompanied by a massive volume ex-
pansion, which destroys the electrode structure as well as the solid
electrolyte interphase (SEI) [67], which is of utmost importance in
cyclability. This volume change is evidently proportional to the size of
the charge carrier (i.e., the reacting ion), and therefore, much more
severe in the case of Na as compared with Li.
Since the material structure is subject to constant change during the
electrochemical reaction, the redox sites do not remain identical. As a
result, conversion material exhibit a pseudocapacitive behaviour rather
than an ideal battery performance, which is expected for intercalation
materials. This is a disadvantage since the energy will be proportional
to the average of the electrode potential and extra care is required to
regulate the cell voltage to deliver a constant voltage. However, all
these disadvantages will be compensated with a high specific capacity.
Various approaches such as utilising a lightweight scaffold have been
used to control the volume change in favour of a better cyclability of
both anode materials [62] and sulphur cathode [68] in lithium-based
systems.
Almost all conversion materials, which have been studied for LIBs,
have also been investigated for NIBs [69–72]. As stated, a successful
development for conversion-based NIB electrode is most likely based on
a success story in LIB because controlling the smaller Li ions is much
easier. However, owing to the different reactivity of Na as compared
with Li, new electrode materials can be developed for the Na-based
conversion. This is indeed similar to the case of alloying with the Al
current collector in which there is a massive difference between Li and
Na.
As we will be discussed later, there are substantial differences be-
tween Li and Na intercalations, but the electrochemical behaviours for
the conversion process are very similar in both cases. Note that the
volume expansion is a matter of performance (to be precise, the
structural stability), but it seems that the underlying mechanisms are
similar regardless of the charge carrier size. As a result, when the Li
conversion is of pseudocapacitive nature, the corresponding Na con-
version exhibits a similar electrochemical behaviour (if not identical)
[73–80]. It should be kept in mind that this is limited to the materials
with an intrinsic pseudocapacitive response, not a deviation from a
battery performance [44]. When the electrochemical response re-
sembles a battery performance with a flat plateau, the difference be-
tween Li and Na systems is distinguishable in terms of energy efficiency.
In these cases, the energy efficiency is much lower for NIB [81].
4. Cathode materials
4.1. Layer metal oxides
Since the commercialisation of LIBs, LiCoO2 has been the dominant
cathode material due to its excellent electrochemical performance.
Although losing its dominance due to the high cobalt cost (and toxi-
city), it is still the most common cathode material of LIBs. The lattice
structure composed of Co and O is among the lightest possible inter-
calation hosts, and thus, the theoretical capacity of LiCoO2 is sig-
nificantly high (ca. 290 mAh g−1). This small lattice arrangement has a
downside, as half of the Li atoms are part of the lattice backbone.
Therefore, the reversible charging is up to Li0.5CoO2. The size of Na
atoms are significantly larger to be accommodated within this light-
weight lattice, and less attention has been paid to NaCoO2 cathodes
despite its old history narrated above. However, recent studies have
revealed the practical potential of NaCoO2. Hwang et al. showed that no
structural breakdown occurs for charging Na0.7CoO2 up to Na0.12CoO2
[82], and thus, the same specific capacity of LiCoO2 can be achieved. It
A. Eftekhari, D.-W. Kim
Fig. 4. (a) Cyclic voltammogram and (b) charge/discharge profiles of a
Na0.7CoO2 electrode. Reproduced with permission from Ref. [83]. Copyright
2017, Wiley-VCH.
should be kept in mind that the electrochemical behaviour of NaCoO2 is
much more complicated than its Li counterpart, and includes several
steps displaying various plateaus at different potentials [83]. Notwith-
standing, as depicted in Fig. 4, the redox peaks in the cyclic voltam-
mogram and the charge/discharge plateaus in the galvanostatic mea-
surements are distinguishable, and the overall electrochemical
behaviour is not of pseudocapacitive nature.
Manganese oxide has always been a promising candidate for energy
storage devices due to its low cost and versatility in the lattice design.
However, the drawbacks of Jahn-Teller effects and solubility of low-
valence manganese have limited the practical development of Mn-based
electrode materials. The tendency for the formation of a one-dimen-
sional structure when reaching the composition of Na0.44MnO2 had
been reported a long time ago [84]. Now, this feature has been em-
ployed to control the direction of diffusion channels [85]. This can
strengthen the diffusion process, but still, the rate capability is below
the practical expectations.
It has been recently described that the presence of water molecules
in the lattice structure strengthens the pseudocapacitive behaviour in
supercapacitors, and this should be considered as a controllable factor
for tuning the energy storage performance [44]. In a similar fashion,
Zhu et al. investigated the impact of this factor on the Na storage ca-
pacity of Na0.33Mn1.67O2, whose electrochemical behaviour is of pseu-
docapacitive nature [86]. The specific capacity was enhanced by over
20%, but in the lack of rate capability investigations, it is difficult to
judge the reason for this enhancement.
4.2. Layered mixed metal oxides
Despite the excellent performance of LiCoO2, there is still a desire to
find better choices having a higher specific capacity and lower cost.
Following the popularity of doping to stabilise the lattice structure,
mixed-metal oxides were considered as more versatile candidates. The
best example of this family is LiMn1/3Ni1/3Co1/3O2, which is about to
overtake the dominance of LiCoO2 in the LIB industry. Tesla Motors/
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Journal of Power Sources 395 (2018) 336–348
Panasonic joint venture which is one of the largest battery manu-
factures has already made this shift. In a similar fashion, sodium mixed-
metal oxides have been considered for NIBs. However, a practical
composition is yet to come. Kim et al. computationally suggested that
Na(Li1/3Mn2/3)O2 can be a promising candidate [87]. Na2/3Fe1/2Mn1/
2O2 seems to be an attractive choice due to its cost but suffers from
long-term instability. Wang et al. prepared an O3-type cathode material
with the composition of Na(Fe1/3Ni1/3Ti1/3)O2, but the cathode could
hardly achieve a specific capacity of 100 mAh g−1 even at slow rates
[88].
A comparative study of Na2/3Ni1/4Mn3/4O2 in a series of mixed Li/
Na electrolytes showed a systematic shift in the electrochemical beha-
viour when changing the Li/Na ration in the electrolyte solution [89].
When increasing the Na concentration, the electrochemical behaviour
tends to a pseudocapacitive response. It has been recently described
that the deviation from a battery performance to a pseudocapacitive
behaviour is due to the energy distribution of the redox sites. Since the
same material had been used for all investigation, the initial energy
levels of the redox sites should be similar [44]. Hence, the intercala-
tion/deintercalation of Na somehow causes a change in the energy level
of subsequently reacting redox sites. This is in agreement with the fact
that increasing the Na concentration results in lower energy efficiency
too [89]. This means excess energy is consumed by the deintercalation
process rather than being supplied.
It was highlighted that the intercalation/deintercalation of Na into
layered manganese oxide occurs via several steps, which appear as
several plateaus in the charge/discharge. Li et al. compared the impact
of Ni and Co dopants [90]. While the presence of Co dopant strengthens
the pseudocapacitive behaviour, Ni dopant tends to form distinguish-
able plateaus [91].
4.3. Potassium metal oxides
In the design of Li intercalation materials, it is common to use Na as
the initial alkali metal. Due to its larger size, the lattice would be more
spacious. Upon ion-exchange during the first charge/discharge cycle,
the Na atoms are replaced with the intercalating Li atoms. The lattice
structure changes but still does not preserve the spacious Na places to
some extent. A similar strategy has been employed for the preparation
of Na intercalating materials. K0.7Fe0.5Mn0.5O2 has been reported to
exhibit an excellent electrochemical performance for the Na storage
[92]. At low charge/discharge rates, the cathode could achieve a spe-
cific capacity of 181 mAh g−1 with an acceptable cyclability over 1000
cycles. In general, a small amount of K can preserve the structural
stability while the Na ions are intercalated/deintercalated [93]. None-
theless, this results in a smaller specific capacity.
4.4. Sodium transition metal phosphates
Lithium transition metal phosphate (LiMPO4) compounds have been
considered as potential cathode materials for LIBs. The main focus is, of
course, on LiFePO4 [94]. For Na intercalation, non-stoichiometric so-
dium iron phosphates have been the subject of investigation [95],
which showed well-defined electrochemical performance but with a
lower redox potential as compared with the Li intercalation/deinter-
calation into/from LiFePO4. However, other members of this family can
provide noticeable properties, e.g., the 5-V performance of LiCoPO4
[96]. A relatively complicated member of this family is Li3V2(PO4)3
(Fig. 5). The complication is because of several phases, which may take
form during the intercalation/deintercalation of Li. This results in the
appearance of several plateaus during the charge/discharge.
Fig. 6 depicts that the discharge performance of Li3V2(PO4)3 is
highly dependent on the level of charging. Note that the phase formed
during the charging process directly affects how the intercalation pro-
ceeds during discharging. Similar studies have been conducted on
Na3V2(PO4)3, which showed a straightforward charging/discharging
A. Eftekhari, D.-W. Kim Journal of Power Sources 395 (2018) 336–348

Fig. 5. Polyhedral representation of the structure of rhombohedral (A) and monoclinic (B) Li3V2(PO4)3. Reproduced with permission from Ref. [133]. Copyright
2014, Elsevier.

the concept of energy efficiency in charge/discharge profiles can be

found here [29]). This suggests that similar to the application of tran-
sition metal phosphates in LIBs, this class of NIB cathode materials
require lattice engineering to facilitate the diffusion process.
Wang et al. synthesised a nanostructured Na3V2(PO4)3 with an ex-
cellent cyclability [100]. In addition to capacity fading, charge/dis-
charge at higher rates results in larger overpotentials and consequently
lower energy efficiency [29]. This phenomenon usually occurs on both
sides (during charging and discharging) for various intercalation sys-
tems including that of Na3V2(PO4)3 [46,47,101–107]. However, the
latter results suggest that the charging plateau remains intact at dif-
ferent rates (Fig. 7). This means that the kinetics of Na extraction is fast
enough and the rate-determining process is indeed Na insertion. Quite
interestingly, an inverse behaviour has been reported for the Na in-
sertion/extraction into/from Na0.67Co0.5Mn0.5O2 where the over-
potentials for the extraction was higher than those for insertion while
increasing the charge/discharge rate [108].
However, the recent attention for Na storage is paid to
NaV2(PO4)2F3 instead [109,110]. There is no noticeable report on the Li
intercalation/deintercalation into/from this compound in the litera-
ture. Ceder and his coworkers reported that a higher specific capacity
could be achieved by replacing two of the F atoms with O atoms [111].
In both cases, the energy efficiency is excellent. In the former case, two
flat plateaus with about 0.5 V difference appear, which tend to close the
gap in the latter compound (Fig. 8).

Fig. 6. The electrochemical voltage composition curves of Li3V2(PO4)3 in the

voltage ranges of (A) 3.0–4.8 and (B) 3.0–4.3 V vs. Li/Li+. Reproduced with
permission from Ref. [133]. Copyright 2014, Elsevier.

with no phase transformation [97,98]. The reason is that only a fraction

of Na is extracted, which is below the threshold of the phase transfor-
mation. The specific capacity achieved is in order of 100–120 mA h g–1.
The key problem with this cathode material is a slow solid-state dif-
fusion. Gao et al. compared the electrochemical performance of
Na3V2(PO4)3 in the form of microparticles and nanofibers, and found Fig. 7. Charge/discharge profiles of a Na3V2(PO4)3 electrode at various charge/
that enlarging the external surface area enhances not only the specific discharge rates from 1 to 50C. Reproduced with permission from Ref. [100].
capacity but also the energy efficiency [99] (further information about Copyright 2017, Royal Society of Chemistry.

343
A. Eftekhari, D.-W. Kim
Fig. 8. (a) Electrochemical curve showing charge and discharge between 2.2
and 4.5 V for Na3V2(PO4)2F3-2yO2y (y = 0 and y = 1), at C/10 rate. (b) Crystal
structure of Na3V2(PO4)2F3-2yO2y (in orthorhombic space group Amam, ap-
plicable for y ≤ 0.2. For y > 0.2, the structure belongs to the tetragonal P42/
mnm space group, where the only significant difference lies in the sodium
distribution). (c) Top view (a-b plane) of the crystal structure for y = 0,
showing the sodium ordering observed in the orthorhombic structure. (d) Top
view (a-b plane) of the crystal structure for y = 1, showing the sodium ordering
observed in the tetragonal structure.
Reproduced with permission from Ref. [132]. Copyright 2017, Wiley-VCH.
4.5. Prussian blue and its analogues
As discussed throughout this paper, most of the candidate materials
for NIBs have been previously used or investigated for LIBs. The family
of transition metal hexacyanoferrates is probably the only class of
electrode materials, which can be used for NIBs but not LIBs. Prussian
blue was the first candidate for the cathode of potassium-ion batteries
(KIBs) [112], and this family of materials is still the dominant choices
for the practical development of KIBs [113]. The attractive advantage is
excellent cyclability of this family for the insertion/extraction of Na and
K cations, guaranteeing a long-term cyclability far beyond any other
choice in the battery research. In terms of the cathode, Prussian blue-
based batteries can be considered as perpetual since the cyclability is
beyond the battery lifetime. Li cannot be reversibly inserted into this
family of electroactive materials, and the lattice begins to break down.
When the size of intercalating ion appropriately matches the diffusion
channels of Prussian blue lattice, the rigid cage-like lattice remains
intact during the insertion/extraction.
The key disadvantage of this family is low specific capacity. The
excellent cyclability comes at the cost of a heavy cage for accom-
modating the charge carrier. However, the excellent electrochemical
performance of Prussian blue and its analogues have kept them as
promising materials in the NIB research [114–118].
5. Electrolytes
An electrolyte obviously plays a critical role to provide a medium
for the transport of sodium ions between anode and cathode. As men-
tioned previously, the cell voltage and energy density are mainly de-
termined by the anode and cathode materials, and thus, more research
attention has been focused on the electrode materials so far. However,
the choice of electrolyte is of particular importance since its char-
acteristics may affect the battery performance in terms of accessible
capacity, operating cell voltage, Coulombic efficiency, rate capability,
cycle life, and battery safety. Among the dominant electrolytes of LIBs
and NIBs, liquid electrolyte [119], ionic liquid electrolyte [120], gel
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Journal of Power Sources 395 (2018) 336–348
polymer electrolyte [121], solid polymer electrolyte [122], and solid
inorganic electrolyte [123] have the central roles. Liquid electrolytes
with lithium or sodium salt dissolved in organic solvents are the most
common choices due to their high ionic conductivity and favourable
interfacial characteristics between the electrolyte and electrode. Ionic
liquid electrolytes composed of asymmetric organic ions are of interest
because of versatility in design and safety. Gel polymer electrolytes
consist of a polymer matrix and liquid electrolyte and exhibit transi-
tional characteristics between liquid and polymer electrolytes. Solid
polymer electrolytes are prepared by dissolving the corresponding salt
in a polymer with high polarity and low glass transition temperature.
Most solid polymer electrolytes are operated at elevated temperatures
to achieve required ionic conductivity. Compared to solid polymer
electrolytes, solid inorganic electrolytes have higher ionic con-
ductivities at the ambient temperature. However, the major obstacles
for practical applications in LIBs and NIBs are poor interfacial char-
acteristics between electrolyte and electrode as well as processability
due to their brittleness. This Section covers only liquid electrolytes that
can practically operate at the room temperature.
5.1. Essential requirements for electrolytes
The characteristics of electrolytes influence the battery perfor-
mance. While there are many types of electrolytes, not all are suitable
for the battery applications. They should have the following char-
acteristics.
5.1.1. Ionic conductivity
Ionic conductivity is one of the most important parameters of the
electrolyte to affect the cycling performance of LIBs or NIBs. Generally,
an electrolyte with higher ionic conductivity shows superior battery
performance. When the batteries are rapidly charged or discharged, the
transport of ions between two electrodes is especially important. The
solid-state electrolytes usually exhibit lower ionic conductivity than
liquid electrolytes. At the ambient temperature, a liquid electrolyte
should have an ionic conductivity higher than 10−3 S cm−1.
5.1.2. Cation transference number
Ionic conductivity is the sum of conductivities of cations and anions
in the electrolyte. Since only the cation (Li+ or Na+) serves as the
charge carrier in LIBs or NIBs, the conductivity of the cation in the
electrolyte should be sufficiently high. The contribution of cations to
the overall ionic conductivity is represented by the cation transference
number. When the cation transference number is low, the cell resistance
increases due to concentration polarisation in the electrolyte. The ca-
tion transference number is influenced by numerous factors including
temperature, the salt concentration, ionic radius, and electric charge.
5.1.3. Electrochemical stability
The electrolyte should be electrochemically stable within the po-
tential range of redox reactions at both anode and cathode sides. The
stable electrochemical window of an electrolyte is defined by the vol-
tage range therein the electrolyte is neither oxidatively nor reductively
decomposed. The stable window controls the operating voltage and
cycling stability of the battery.
5.1.3. Chemical stability
The electrolyte should be chemically stable towards various battery
components such as the electrode materials including the active ma-
terial, the polymeric binder, separator, current collector, and other
additives. No chemical reactions should occur within the cell during the
cell operation.
5.1.4. Thermal stability and safety
Organic electrolytes are easily decomposed during the cell operation
at high temperature, which results in a rapid capacity loss. Most of the
A. Eftekhari, D.-W. Kim Journal of Power Sources 395 (2018) 336–348

Table 1 and PC rather than using PC alone exhibited better cycling stability in
Physical properties of organic solvents used in preparing liquid electrolytes for the hard carbon-based anode, since EC could form a more stable and
LIBs and NIBs. conductive SEI at low potentials [126]. Vidal-Abarca et al. reported that
Solvent Tm/°C Tb/°C Dielectric Viscosity/cP 1 M NaPF6 in EC/DEC showed higher discharge capacity and better
constant capacity retention than the cell using 1 M NaPF6 in PC since the PC was
unstable at lower voltages [127].
Ethylene carbonate (EC) 37 248 89.6 1.86a
Propylene carbonate (PC) −49 242 64.9 2.53
1,2-Butylene carbonate (BC) −45 250 55.9 3.18 5.2.2. Salts
Dimethyl carbonate (DMC) 5 90 3.1 0.59 The type of salts dissolved in organic solvents also affects the
Diethyl carbonate (DEC) −43 127 2.8 0.75 electrochemical properties of electrolytes. Anions with larger radii are
Ethylmethyl carbonate (EMC) −55 108 2.9 0.65
favoured since sodium salts having delocalized anions tend to dissociate
Dimethoxyethane (DME) −58 85 7.2 0.46
Diethyeneglycol dimethylether −64 162 7.4 1.06
more readily. Sodium salts usually have a higher melting point than
(DEGDME) lithium salts indicating their higher thermal stability and enhanced
Tetraethyeneglycol −30 275 7.8 4.05 safety as compared to their lithium equivalents [128]. Among various
dimethylether (TEGDME) types of sodium salts for NIBs reported so far, NaClO4 is the most
Tetrahydrofuran (THF) −109 65 7.3 0.46
commonly used salt at the lab scale despite its safety issues due to
1,3-Dioxolane (DOL) −95 78 6.8 0.58
γ-Butyrolactone (BL) −42 206 39.1 1.75 strong oxidant nature of ClO4−. Salts such as NaPF6 and NaBF4 that
contain fluorinated Lewis acids are also commonly used in NIBs because
a
Measured at 40 °C. of their high solubility and chemical stability. However, NaBF4 is less
conductive due to strong interactions between cations and anions,
organic solvents used in LIBs and NIBs are flammable and may cause while the use of NaPF6 at elevated temperatures causes a thermal de-
fire or explosions at elevated temperatures. Thus, the thermal stability composition and results in hydrolysis to yield PF5, POF3 and HF in the
of electrolyte is a key factor to influence the high-temperature cycling presence of moisture.
stability and battery safety. In order to assure the battery safety, non- Imide salts such as sodium bis(trifluoromethanesulfonyl)imide
flammable electrolyte materials are favoured. The electrolyte should (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI) have also been
also have low toxicity in case of leakage or disposal. used for NIBs due to their non-toxicity and higher thermal stability than
NaPF6 and NaBF4, though they could not be used as a single salt due to
5.1.5. Cost Al corrosion. Bhide et al. compared the physicochemical properties of
Even if the electrolyte has superior characteristics, it may be diffi- liquid electrolytes based on NaPF6, NaClO4 and NaCF3SO3 salts in the
cult to be used in batteries, if the cost is high. When considering the cost binary mixture of EC and DMC [129]. The maximum conductivities
advantage of NIB compared to LIB, expensive electrolytes are unlikely obtained were 6.8 mS cm−1 for 0.6 M NaPF6 and 5.0 mS cm−1 for 1.0 M
to be adopted in NIBs. NaClO4. They reported that NaPF6–EC/DMC was a favourable electro-
lyte for the formation of a stable surface film and the reversibility of the
5.2. Components of liquid electrolytes for NIBs Na0.7CoO2 cathode material. A new electrolyte salt, sodium-difluoro
(oxalato)borate (NaDFOB), was synthesised and studied, which showed
5.2.1. Solvents high capacity and good rate capability in a Na/Na0.44MnO2 cell [130].
Liquid electrolytes for NIBs are made by dissolving sodium salts in NaDFOB salt exhibited good compatibility and stability with various
organic solvents containing small amounts of additives. Representative organic solvents used in NIBs and generated no toxic or dangerous
physical properties of organic solvents commonly used in NIBs are products when exposed to air and water.
summarised in Table 1. Two major characteristics of organic solvents
that determine ionic conductivity are dielectric constant and viscosity. 5.2.3. Additives
While high dielectric constant and low viscosity are required for the The primary role of additives is to enhance the battery performance
liquid electrolyte to possess high ionic conductivity, higher dielectric and safety. Most liquid electrolytes used in LIBs and NIBs contain small
constant leads to increased viscosity. This can be solved by mixing quantities of additives. There are a variety of additives including SEI-
solvents with a high dielectric constant and those with a low viscosity. forming additives, overcharge inhibitors, flame retardants, radical
As given in Table 1, cyclic carbonates such as ethylene carbonate (EC) scavengers and fluidity enhancers. Among various types of additives,
and propylene carbonate (PC) have high dielectric constant and high many research works have been mainly focused on SEI-forming ad-
viscosity due to large interactions within solvent molecules. In contrast, ditives. The sodium intercalation with carbonaceous anode materials
linear carbonates such as dimethyl carbonate (DMC) and diethyl car- such as HC takes place at low potentials close to that of Na/Na+. Hence,
bonate (DEC) have low dielectric constant and low viscosity. Thus, high stability against reduction is one of the necessary conditions for
cyclic carbonates and linear carbonates are usually mixed to obtain electrolytes of NIBs. Accordingly, a protecting surface film, which is
desirable characteristics as organic solvents for NIBs. permeable for sodium ions but electronically insulating, should be
Ponrouch et al. reported that mixed solvent-based electrolytes ex- formed on the anode during the initial stage of charging. The protective
hibited higher conductivity and better cycling characteristics than film viz. SEI suppresses further solvent decomposition and plays a
single carbonate- or ether-based electrolytes [124]. A comprehensive beneficial role in improving the cycling stability of NIBs. Type or con-
study has also been reported by the same group entailing optimisation tent of additives directly influences the chemical composition of the SEI
of electrolyte formulation and compatibility studies with electrode layer formed on the anode. However, there are only a few reports on the
materials [125]. They reported that adding 10% DMC to EC/PC mixture SEI formation mechanism in the NIB electrolytes. Komaba et al. in-
resulted in a decrease in viscosity and enhanced ionic conductivity. EC/ vestigated the cycling performance of NIBs with several SEI-forming
PC/DMC (45/45/10) was the optimum composition resulting in sa- additives, such as fluoroethylene carbonate (FEC), trans-difluoroethane
tisfactory rate capability and high capacity during cycling. The opti- carbonate (DFEC), ethylene sulfite (ES) and vinylene carbonate (VC),
misation of electrolyte formulation should consider not only ionic which are well-known additives for LIBs [131]. They reported that FEC
conductivity but also interfacial characteristics between electrode and was the most effective additive to improve the reversibility of electro-
electrolyte. A reduction of organic solvents on the surface of anode chemical sodium insertion for NIB comprising of HC anode and NaNi1/
results in the formation of SEI, which significantly affects the cycling 2Mn1/2O2 cathode.
characteristics of NIBs. In this respect, a mixed solvent consisting of EC Overall, the type and composition of electrolytes significantly

345
A. Eftekhari, D.-W. Kim
influence the battery performance and safety. Although different types
of electrolyte formulation including new sodium salts and noble ad-
ditives have been reported, extensive research still needs to be done by
developing new components and optimising the formulation to make
NIBs to be commercialised in the near future.
6. Concluding remarks
NIB has been subject to numerous research studies lately. Although
it is considered as an economical replacement to the current LIBs, the
strategy of research should be adjusted to target potential applications
of NIBs due to their unique features. The cost or scarcity of Li is not a
sufficient reason for replacing the successful LIBs with NIBs, which are
still far from practical energy storage devices. On the other hand, the
disadvantages of NIB such as specific capacity have been exaggerated in
the literature. When assembling a full cell including constant compo-
nents such as current collectors, there is no significant (at least not at
the level usually narrated in the literature) advantage for LIB. The
importance of this point is that if considering the weight of the charge
carrier as a disadvantage, then, there is no solution to make NIBs
competitive. The prime issue of the current NIBs is the lack of light-
weight materials (note that we need lightweight hosts rather than
lightweight charge carriers).
In a narrative comparison between similar materials, which have
been widely investigated in both LIBs and NIBs, it was discussed that
the intercalation/deintercalation of Na is usually much more compli-
cated than the corresponding phenomena for Li. This clearly indicates
that we need a profound understanding of the solid-state electro-
chemistry of Na intercalation materials, but the majority of current
research studies are focused on the examination of typical materials
with the hope for experimental discoveries. Instead, Na intercalation
should be compared with Li intercalation to fathom the limiting factors,
which keep the Na materials behind the Li counterparts. Based on re-
presentative comparisons of these two sister systems, it was highlighted
that the key issue is the complicated Na intercalation. Therefore, the
NIB electrode materials should be subtly designed by inspecting various
stages of the charge/discharge via in situ techniques. In other words, the
overall comparison of LIB and NIB similar systems is not helpful, and
the focus should be on tiny steps, which differentiate the corresponding
intercalation processes.
In the case of conversion materials, we are far from any practical
development since none has yet been achieved the satisfactory perfor-
mance even for lithium batteries (including Li−S batteries). Since Na
ions are much bigger than Li ions, the volume expansion and the
complexity of the structural changes are much more severe. It is un-
likely to develop practical convention materials for NIBs before
achieving a practical design for LIBs since the conversion mechanism is
simpler when Li is involved.
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