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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 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
1.1. Historical background some ideas became the centre of attention. For instance, metal-sulphur
batteries were subject of numerous investigations. At the preliminary
The history of sodium-ion batteries (NIBs) backs to the early days of stage, the key requirement was to design a working system rather than
lithium-ion batteries (LIBs) before commercial consideration of LIB, but maximising the specific energy by a lightweight charge carrier.
sodium charge carrier lost the competition to its lithium rival because Therefore, the focus was on sodium-sulphur battery [3] rather than the
of better choices of intercalation materials for Li. During the 1960s, lithium-sulphur counterpart.
various electrochemical reactions were utilised for designing batteries, In the late 1970s, the boundary of solid state science and electro-
but most of these ideas did not survive for more than a few years. The 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 Journal of Power Sources 395 (2018) 336–348

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

1.2. Li vs Na: a realistic comparison Despite the usual abundance of lighter elements, the natural re-
sources for lithium are 1/1000 less than those of sodium. This has been
Owing to the rapidly growing interest in NIBs, it is common in the initially considered as the prime motive for the development of NIBs, as
literature to compare NIBs with the available LIBs to highlight the ad- it is still frequently repeated in the literature. For instance, a brief note
vantages and disadvantages of NIBs. However, most of the statements calling lithium the new gold is among the highly cited papers of the
are unrealistic and do not lead us very far. Therefore, it is of vital im- field [31]. It is true that sodium is cheaper than lithium, but the cost of
portance to clarify a realistic outlook for the future of NIBs. The key the charge carrier has a minor impact on the overall cost of a battery
point is that a cell is composed of various components whose weights since the other components are more expensive, and a significant cost

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

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A. Eftekhari, D.-W. Kim Journal of Power Sources 395 (2018) 336–348

lithium. Furthermore, recent market research suggested that the price 2. General trends in the choice of materials
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 current materials of NIBs are almost the same range of mate-
the supply to meet the rising demand. It was indeed because of an rials, which have been investigated during the past four decades in LIBs.
unusual synchronisation of various factors such as environmental reg- Kim et al. made a statistical analysis of publications during the past
ulations for reducing CO2 emission, governmental policies for shifting years [42]. They showed that the majority of works on cathode mate-
to electric vehicles, the market success of electric vehicles and new rials are limited to layered metal oxides and polyanionic compounds,
automakers such as Tesla Motors. Notwithstanding, it is unlikely to while Prussian blue and its analogues are marginally studied. On the
witness such 'unpredicted' rise in the demand again. anode side, the focus is on carbon materials and metal oxides, while the
Second, the natural resources of lithium are way higher than what is marginal attention is paid to Na alloys. Owing to the success of inter-
usually considered as the limit of supply [36]. During the last 10 years, calation materials with rigid lattice structure in LIBs, less attention was
the estimation of the lithium resources by the US Geographical Surveys paid to organic host materials. However, further attention is being paid
was increased by over 300%. On the other hand, the increasing demand to the Na counterparts in the absence of ideal intercalation choices. Xu
will justify exploitation of new resources [37]. Most discussions about et al. have recently reviewed the organic materials for NIBs in great
the lithium resources are limited to the easy-to-exploit brane resources detail [43].
located in the so-called lithium triangle in South America. Even in the Owing to the popularity of nanostructures, there is a tendency for
latter case, Bolivia with the largest resources of three countries (Bolivia, preparing the electroactive materials in various nanostructured forms.
Chile, Argentina) has not yet started to exploit lithium (at a consider- The advantage in battery systems is a shorter solid-state diffusion
able scale) [38]. 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
1.5. Motives and strategy of research higher surface area results in the possibilities of structural irregularities,
which can broaden the redox potential. The latter phenomenon is in-
As discussed in Sections 1.3 and 1.4, the motives for developing deed the deviation form battery performance to pseudocapacitive be-
NIBs is neither cost nor scarcity of lithium. Although they have a po- haviour [44]. There are several other disadvantages of nanomaterials
sitive impact, they are not sufficient motives for the development of for energy storage applications such as low tap density. Hence, nanos-
NIBs since LIBs can fairly meet the growing demand. LIBs have a rich tructured materials could not find a dominant role in the design of
history of research, which is the prime advantage for the current battery materials.
technological development and a disadvantage from the innovation However, nanomaterials can provide an extra advantage in the case
perspective. It is unlikely (or more precisely, very slow) to find new of NIBs. Since Na ions are larger than Li ions, the intercalation of Na
opportunities in LIBs. into small lattice structures (which are desirable for high-energy bat-
NIB has its own domain of research, which can provide a broad teries) might be accompanied by structural and volume change.
range of new possibilities. The common mistake is to treat NIB as a Utilising nanostructured architecture provides space to accommodate
replacement to LIB. Therefore, as it will be reviewed in the present the expanding volume [45]. Fig. 2 illustrates typical roles of the na-
paper, the successful cases of LIBs are usually adopted for the devel- noporosity for accommodating the large intercalating Na ions. This
opment of NIBs. Nonetheless, NIBs can be developed based on mate- strategy has been used to place the electroactive materials over a na-
rials, which are not considered in LIBs. For instance, Prussian blue and nostructured scaffold where space is supplied [46–48].
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 3. Anode materials
performance of Li insertion/extraction. Na could be inserted/extracted
into/from Prussian blue for tens of thousands of cycles [40], the cy- One of the key challenges of NIBs is the anode material. For almost
clability which is very uncommon for any Li system. This is the reason three decades, the dominated anode material in the commercial LIBs
that Prussian blue and its analogues are among the common candidates has been graphite. Although potassium-ion batteries (KIBs) can employ
for NIBs, but this is still an old idea. What the NIB development needs graphite anodes, intercalation of Na into graphite is thermodynamically
are new ideas. unfavourable [49]. Despite the unsuitability of graphite for NIBs, gra-
The strategy of research is not very progressive. A majority of works phite is too enticing to be totally eliminated. Therefore, numerous
are devoted to the composition of electrode materials for improving the works have done to alter the solid-state electrochemistry of graphite for
electrochemical performance of common electrode materials. At this the Na intercalation. The most promising approach is to co-intercalate
stage, most of the available candidates cannot provide satisfactory the solvent to make the Na intercalation possible [33,50]. Despite the
performance for the practical development. Hence, it is useless to im- excellent electrochemical performance, this approach has two major
prove them slightly. Instead, the current focus should be on the fun- issues: (i) the co-intercalation can be conducted in an ether-based
damental understanding of the solid-state electrochemistry of Na in- electrolyte. This means losing the key advantages of carbonate-based
tercalation to subtly design the electrode materials. In fact, the current electrolytes, which have been the dominated electrolyte of LIBs since
quest is for finding or engineering electroactive materials rather than the commercialisation. (ii) The co-intercalation of another species
improving them. In this regard, we should learn from the Li systems but means that half of the graphite capacity cannot be exploited for the
not copy them, since they are substantially different, as will be dis- energy storage purpose, as the intercalated ether is not a charge carrier
cussed in the following sections. (Fig. 3). There is no major difference between the capacity attained by
In the case of sulphur batteries, as mentioned above, the history of Li or Na intercalation. An interesting feature is that the electrochemical
Na−S was even richer. When considering emerging batteries such as performance of Na is better than Li in terms of energy efficiency [29], as
selenium batteries [41], there is no historical advantage of Li−Se the hysteresis between the charge and discharge profiles is much
battery over Na−Se battery, but still, the tendency is towards the smaller for Na intercalation. This means lower overpotentials are re-
Li−Se battery. This is mostly due to the prospect of LIBs rather than quired for the intercalation/de-intercalation of Na as compared with
technical reasons. Therefore, Na batteries should be explored within that of Li. Nonetheless, the current status of graphite anodes does not
their own domains rather than replacements of Li counterparts, as there satisfy the practical requirements.
is still no solid ground to justify this replacement.

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A. Eftekhari, D.-W. Kim Journal of Power Sources 395 (2018) 336–348

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 current collector [57,61]. As quoted above, a noticeable advantage of
NIBs is the possibility of utilising an Al current collector for the anode.
Hard carbon (HC) is among the most promising anode materials for In the latter design, no anode material is used, and the charge carrier
NIBs [51–53], but it has rarely been investigated for LIBs since graphite after deintercalation of the cathode during charging is electroplated on
anode perfectly works for the latter. Therefore, our knowledge about the current collector. This cell structure is theoretically the ultimate
intercalation into HC does not have a long history, and recent reports design for the anode since the anode capacity cannot be enhanced any
have exhibited the practical potentials. Albeit, HC has also been tested further. However, the system is too complicated with various new
as a potential anode material in LIB, but there are a limited number of considerations, which should be taken into account such as the possi-
works [54] including those using HC as a conducting agent for the bility of dendrite formation, anomaly of the electrode/electrolyte in-
cathode [55]. Various HC samples have been prepared from different terface, etc. On the other hand, the presence of metallic Na in the
natural products, and thus, it is not easy to compare the results reported charged state can cause the same safety concerns due to its chemical
in the literature. In almost all cases, the carbonisation temperature has reactivity. For instance, the battery damage at the charged state can
an enormous impact on the electrochemical performance of the re- easily cause an explosion as a result of contact with water or moisture.
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 3.3. Titanate spinel
[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 Although having a relatively high potential vs Li/Li+, Li4Ti5O12 is
a full cell, the rate capability is much higher than the fundamental among the promising candidates of anode materials due to its excellent
studies. This suggests that the practical potential of HC anodes might be performance. This anode material delivers a close-to-perfect flat pla-
more than what already reported in the literature. 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/
3.2. Metallic sodium deintercalation. Owing to the larger size of Na ions, the electrochemical
performance is no longer ideal. A considerable behaviour is that the
Utilising the charge carrier as a metallic anode is beneficial in terms overall anode potential is slightly lower for the Na intercalation system
of energy density as the maximum cell voltage and minimum anode size [63–65]. The latter feature is of utmost importance as elevated the cell
can be achieved. However, since the commercialisation of LIB, metallic voltage, which can close the gap between the operating voltages of LIB
Li anode has never been considered as a potential anode (though there and NIB. This is directly in favour of the energy density discussed
were some early commercial LIBs employing Li anodes) due to the above. However, the cyclability is significantly poorer for the Na in-
safety issues. However, recent advancements have provided an oppor- tercalation while a noticeably lower capacity is achieved [65]. The
tunity for reconsidering the metallic Li anode [59,60]. This possibility is latter issue is not due to the weight of Na but anomalous intercalation,
weaker in the case of NIB because the chemical reactivity of Na is which causes a deviation from the characteristic ideal battery perfor-
higher and the safety concern is more severe. However, this has not mance of Li4Ti5O12.
fully eliminated this anode from the NIB research. This difference between Li and Na intercalations occurs for almost
An interesting form of metallic Ni anode is the so-called anode-free all metal oxide anode materials [66]. In other words, this phenomenon
cell in which Na can be reversibly plated/stripped onto/from the Al is associated with the intercalation of larger Na ions within the compact

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A. Eftekhari, D.-W. Kim 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
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 4.1. Layer metal oxides
cells is given versus Li/Li+ and Na/Na+, Reproduced with permission from Ref.
[50]. Copyright 2014, Wiley-VCH.
Since the commercialisation of LIBs, LiCoO2 has been the dominant
cathode material due to its excellent electrochemical performance.
lattice of metal oxides. As will be described later for spacious lattice Although losing its dominance due to the high cobalt cost (and toxi-
structures such as those of transition metal hexacyanoferrates, the Na city), it is still the most common cathode material of LIBs. The lattice
intercalation is more favourable. In fact, a design of the appropriate structure composed of Co and O is among the lightest possible inter-
intercalation materials for NIBs requires appropriate diffusion channels, calation hosts, and thus, the theoretical capacity of LiCoO2 is sig-
which are substantially different from those of counterpart Li-based nificantly high (ca. 290 mAh g−1). This small lattice arrangement has a
materials. 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
3.4. Conversion materials atoms are significantly larger to be accommodated within this light-
weight lattice, and less attention has been paid to NaCoO2 cathodes
Conversion-based electrode materials are usually in the elemental despite its old history narrated above. However, recent studies have
forms or simple compounds since the electrochemical reaction is based revealed the practical potential of NaCoO2. Hwang et al. showed that no
on low oxidation states. Therefore, almost all conversion-based mate- structural breakdown occurs for charging Na0.7CoO2 up to Na0.12CoO2
rials are targeted for anodes due to their low redox potentials. Contrary [82], and thus, the same specific capacity of LiCoO2 can be achieved. It

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A. Eftekhari, D.-W. Kim 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
Fig. 4. (a) Cyclic voltammogram and (b) charge/discharge profiles of a several plateaus in the charge/discharge. Li et al. compared the impact
Na0.7CoO2 electrode. Reproduced with permission from Ref. [83]. Copyright of Ni and Co dopants [90]. While the presence of Co dopant strengthens
2017, Wiley-VCH. the pseudocapacitive behaviour, Ni dopant tends to form distinguish-
able plateaus [91].
should be kept in mind that the electrochemical behaviour of NaCoO2 is
much more complicated than its Li counterpart, and includes several 4.3. Potassium metal oxides
steps displaying various plateaus at different potentials [83]. Notwith-
standing, as depicted in Fig. 4, the redox peaks in the cyclic voltam- In the design of Li intercalation materials, it is common to use Na as
mogram and the charge/discharge plateaus in the galvanostatic mea- the initial alkali metal. Due to its larger size, the lattice would be more
surements are distinguishable, and the overall electrochemical spacious. Upon ion-exchange during the first charge/discharge cycle,
behaviour is not of pseudocapacitive nature. the Na atoms are replaced with the intercalating Li atoms. The lattice
Manganese oxide has always been a promising candidate for energy structure changes but still does not preserve the spacious Na places to
storage devices due to its low cost and versatility in the lattice design. some extent. A similar strategy has been employed for the preparation
However, the drawbacks of Jahn-Teller effects and solubility of low- of Na intercalating materials. K0.7Fe0.5Mn0.5O2 has been reported to
valence manganese have limited the practical development of Mn-based exhibit an excellent electrochemical performance for the Na storage
electrode materials. The tendency for the formation of a one-dimen- [92]. At low charge/discharge rates, the cathode could achieve a spe-
sional structure when reaching the composition of Na0.44MnO2 had cific capacity of 181 mAh g−1 with an acceptable cyclability over 1000
been reported a long time ago [84]. Now, this feature has been em- cycles. In general, a small amount of K can preserve the structural
ployed to control the direction of diffusion channels [85]. This can stability while the Na ions are intercalated/deintercalated [93]. None-
strengthen the diffusion process, but still, the rate capability is below theless, this results in a smaller specific capacity.
the practical expectations.
It has been recently described that the presence of water molecules 4.4. Sodium transition metal phosphates
in the lattice structure strengthens the pseudocapacitive behaviour in
supercapacitors, and this should be considered as a controllable factor Lithium transition metal phosphate (LiMPO4) compounds have been
for tuning the energy storage performance [44]. In a similar fashion, considered as potential cathode materials for LIBs. The main focus is, of
Zhu et al. investigated the impact of this factor on the Na storage ca- course, on LiFePO4 [94]. For Na intercalation, non-stoichiometric so-
pacity of Na0.33Mn1.67O2, whose electrochemical behaviour is of pseu- dium iron phosphates have been the subject of investigation [95],
docapacitive nature [86]. The specific capacity was enhanced by over which showed well-defined electrochemical performance but with a
20%, but in the lack of rate capability investigations, it is difficult to lower redox potential as compared with the Li intercalation/deinter-
judge the reason for this enhancement. 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
4.2. Layered mixed metal oxides (Fig. 5). The complication is because of several phases, which may take
form during the intercalation/deintercalation of Li. This results in the
Despite the excellent performance of LiCoO2, there is still a desire to appearance of several plateaus during the charge/discharge.
find better choices having a higher specific capacity and lower cost. Fig. 6 depicts that the discharge performance of Li3V2(PO4)3 is
Following the popularity of doping to stabilise the lattice structure, highly dependent on the level of charging. Note that the phase formed
mixed-metal oxides were considered as more versatile candidates. The during the charging process directly affects how the intercalation pro-
best example of this family is LiMn1/3Ni1/3Co1/3O2, which is about to ceeds during discharging. Similar studies have been conducted on
overtake the dominance of LiCoO2 in the LIB industry. Tesla Motors/ Na3V2(PO4)3, which showed a straightforward charging/discharging

342
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.

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A. Eftekhari, D.-W. Kim 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.
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 5.1. Essential requirements for electrolytes
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/ The characteristics of electrolytes influence the battery perfor-
mnm space group, where the only significant difference lies in the sodium mance. While there are many types of electrolytes, not all are suitable
distribution). (c) Top view (a-b plane) of the crystal structure for y = 0, for the battery applications. They should have the following char-
showing the sodium ordering observed in the orthorhombic structure. (d) Top acteristics.
view (a-b plane) of the crystal structure for y = 1, showing the sodium ordering
observed in the tetragonal structure. 5.1.1. Ionic conductivity
Reproduced with permission from Ref. [132]. Copyright 2017, Wiley-VCH.
Ionic conductivity is one of the most important parameters of the
electrolyte to affect the cycling performance of LIBs or NIBs. Generally,
4.5. Prussian blue and its analogues an electrolyte with higher ionic conductivity shows superior battery
performance. When the batteries are rapidly charged or discharged, the
As discussed throughout this paper, most of the candidate materials transport of ions between two electrodes is especially important. The
for NIBs have been previously used or investigated for LIBs. The family solid-state electrolytes usually exhibit lower ionic conductivity than
of transition metal hexacyanoferrates is probably the only class of liquid electrolytes. At the ambient temperature, a liquid electrolyte
electrode materials, which can be used for NIBs but not LIBs. Prussian should have an ionic conductivity higher than 10−3 S cm−1.
blue was the first candidate for the cathode of potassium-ion batteries
(KIBs) [112], and this family of materials is still the dominant choices 5.1.2. Cation transference number
for the practical development of KIBs [113]. The attractive advantage is Ionic conductivity is the sum of conductivities of cations and anions
excellent cyclability of this family for the insertion/extraction of Na and in the electrolyte. Since only the cation (Li+ or Na+) serves as the
K cations, guaranteeing a long-term cyclability far beyond any other charge carrier in LIBs or NIBs, the conductivity of the cation in the
choice in the battery research. In terms of the cathode, Prussian blue- electrolyte should be sufficiently high. The contribution of cations to
based batteries can be considered as perpetual since the cyclability is the overall ionic conductivity is represented by the cation transference
beyond the battery lifetime. Li cannot be reversibly inserted into this number. When the cation transference number is low, the cell resistance
family of electroactive materials, and the lattice begins to break down. increases due to concentration polarisation in the electrolyte. The ca-
When the size of intercalating ion appropriately matches the diffusion tion transference number is influenced by numerous factors including
channels of Prussian blue lattice, the rigid cage-like lattice remains temperature, the salt concentration, ionic radius, and electric charge.
intact during the insertion/extraction.
The key disadvantage of this family is low specific capacity. The 5.1.3. Electrochemical stability
excellent cyclability comes at the cost of a heavy cage for accom- The electrolyte should be electrochemically stable within the po-
modating the charge carrier. However, the excellent electrochemical tential range of redox reactions at both anode and cathode sides. The
performance of Prussian blue and its analogues have kept them as stable electrochemical window of an electrolyte is defined by the vol-
promising materials in the NIB research [114–118]. tage range therein the electrolyte is neither oxidatively nor reductively
decomposed. The stable window controls the operating voltage and
5. Electrolytes cycling stability of the battery.

An electrolyte obviously plays a critical role to provide a medium 5.1.3. Chemical stability
for the transport of sodium ions between anode and cathode. As men- The electrolyte should be chemically stable towards various battery
tioned previously, the cell voltage and energy density are mainly de- components such as the electrode materials including the active ma-
termined by the anode and cathode materials, and thus, more research terial, the polymeric binder, separator, current collector, and other
attention has been focused on the electrode materials so far. However, additives. No chemical reactions should occur within the cell during the
the choice of electrolyte is of particular importance since its char- cell operation.
acteristics may affect the battery performance in terms of accessible
capacity, operating cell voltage, Coulombic efficiency, rate capability, 5.1.4. Thermal stability and safety
cycle life, and battery safety. Among the dominant electrolytes of LIBs Organic electrolytes are easily decomposed during the cell operation
and NIBs, liquid electrolyte [119], ionic liquid electrolyte [120], gel at high temperature, which results in a rapid capacity loss. Most of the

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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 Journal of Power Sources 395 (2018) 336–348

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