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Sodium and Sodium-Ion Batteries: 50 Years of Research

Claude Delmas
Among the various ways to store elec-
This paper gives an overview of the research carried out on sodium batteries tricity on a large scale, three can be
in the last 50 years. The discovery of the very high Na+ ion conductivity considered:
in β-Al2O3 opened the way to high-energy batteries (sodium/sulfur and - Pumped-Storage of Water: It is the most
sodium/NiCl2) for load leveling and electrical vehicles. Then, the liquid efficient; it is developed in very large
electrolyte batteries were considered with intercalation-based electrodes and scale capacity storage facilities which
lithium and sodium as mobile ions. When Sony proposed the lithium-ion require specific sites; nevertheless, in
the future due to its long lifetime it will
batteries, most research moved to lithium systems, exhibiting a higher
play a significant role for intermediate
energy density. These are now currently used in electronic devices, hybrid time storage of a few hours to several
electrical vehicle (HEV) and electrical vehicle (EV). The development of days, and even for intermediate scale
renewable energies, which have an intermittent character, requires very capacity energy storage.
large batteries for frequency regulation and peak production shift. For these - Electrochemical Energy Storage in Bat-
teries: It is now used locally in some
stationary applications the most important parameters are the lifetime, the
places that are not connected to the elec-
power, the price, and the material availability. Since sodium ion batteries are tricity network and on the smart grids
able to satisfy these criteria, these new material families now concern a large for frequency regulation or small peak
part of the scientific community. This article gives a general introduction and production shifts. Examples include
an overview of the research carried out on the materials that are presented sodium sulfur batteries (NaS) which
in detail, in the articles within this special issue on sodium batteries. are used in Japan; redox flow batteries
under development, and some large
scale lithium–ion batteries (LIBs) that
are used in specific places.
1. Introduction - Storage via Hydrogen: The development of hydrogen as a
way of using fuel cells is considered and seems very inter-
The problems of climate change due to the greenhouse effect
esting from the pollution point of view at the local scale.
and depletion of natural resources require a reduction in our con-
From the technical point of view, most of the problems are
sumption of fossil fuels. For several decades, nuclear energy was
almost solved. Nevertheless, hydrogen has to be produced
considered as the solution for the future of electricity production.
and stored; and in this case, the yield is quite low, similar
Because of the safety issues of this technology, in many countries
to that of the internal combustion engine. Electricity storage
in the world, there is a tendency to limit the part of the electricity
via hydrogen requires water electrolysis, H2 gas storage, and
produced by nuclear plants. The only way to overcome those prob-
electricity production in fuel cells, all of which leads to a low
lems consists of developing renewable energy sources: hydroelec-
efficiency and therefore, significant energy loss during elec-
tricity plants, wind, and solar farms. One of the main interests of
tricity storage.
these technologies concerns their delocalization, which allow for
electricity production close to the utilization place without any pol- In the last 15 years with the development of portable elec-
lution or security problems. However, the main drawback of wind tronic devices (laptops, cellular phones tablets, etc.) the
power and photovoltaic energy is their intermittent characters; the production of lithium-ion batteries in the world became very
production fluctuations are on the order of hours, days, or weeks important. More recently, because of the pollution problems
for wind power and of minutes and hours for photovoltaics. More- associated with the use of cars with internal combustion
over, photovoltaic panels produce electricity at a value close to the engines and their CO2 emission, the development of hybrid
nominal value (peak current) only when the sun shines around and electric vehicles was promoted. This requires batteries with
noon, far from the maximum day consumption peak. For the con- high gravimetric and volumetric energy. Therefore, all over the
sumer, electricity is the most convenient easy source to use, but world there is a need to increase the number of large factories
one has to balance supply and demand in real time. to product these batteries. LIBs have to be optimized to satisfy
electrical vehicle (EV) producer requirements concerning
Dr. C. Delmas their capacity, lifetime, safety, and price. Even if most of these
ICMCB-CNRS requirements can be fulfilled by science and technology, prob-
87, Av Dr A. Schweitzer, 33608 Pessac, France lems with the availability of lithium in the earth’s crust will arise
E-mail: [email protected]
and will lead to a strong increase in the price. The lithium raw
The ORCID identification number(s) for the author(s) of this article
materials availability, in limited extent, to a few countries in the
can be found under https://doi.org/10.1002/aenm.201703137.
world is a problem that must be considered. This would restrict
DOI: 10.1002/aenm.201703137 to use LIBs mainly for mobile systems: electronics and vehicles.

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For stationary applications, the main parameters of the cells

which have to be considered are: price ($ W h−1 kg−1), lifetime Claude Delmas, CNRS
(years, cycle number), and power (W kg−1). This requires raw research director, is a Solid
materials with an abundant availability (low price). For this State Chemist working in
reason, sodium batteries are considered. The global sodium the field of positive electrode
reserves can be considered as infinite. The development of materials for secondary
sodium batteries is constrained by the discovery of new posi- batteries. His expertise
tive electrode materials with cheap and abundant elements like concerns layered oxides and
manganese and iron. phosphates able to interca-
late reversibly sodium and
lithium. During his career,
he synthesized many new
2. The History
materials and he studied their
Faraday observed the ionic conductivity in the solid state (PbF2 structural and physical properties. He proposed a general
and Ag2S) at high temperature for the first time in 1839. This classification of the layer oxides, which is now used by all
discovery inspired several other researchers: Warburg shows the scientific community working in this field.
the Na+ conductivity in Thüringe glasses in 1884. Fundamental
contribution was added by Nernst who proposed the well-
known Nernst equation; he showed the ionic conductivity in must be stable for a very long time at high temperature in very
doped Zirconia and in 1897 developed the first application in reactive conditions. Several companies worked for a long time
the Nersnt lamp (with a zirconia filament) which was one of without success to obtain the lifetime required applications. At
the first incandescent lamps. In the first part of the 20th cen- the beginning, this technology concerned EV’s; it was sold to
tury Frenkel, Schottky, Wagner, and Krüger contribute to the the Japanese company NGK that succeeded after many years to
basis of the solid state electrochemistry which was called Solid develop a system for stationary applications (peak leveling). In
State Ionics in 1967 by Takahashi. 2007, 165 MW h of capacity was operating for grid stabilization.
The discovery by Kummer and Yao of high Na+ ion conduc- They are currently still in operation.
tivity at intermediate temperatures opened new perspectives A derivative of this battery using β-Al2O3 (or β″-Al2O3) as
for applications.[1]β-Al2O3, known from the 1930s, is a non- solid electrolyte was developed in South Africa; the ZEBRA
stoichiometric compound existing in the composition range (ZEolite Battery Research Africa) battery invented by Coetzer
(5.3 Al2O3, Na2O–8.5 Al2O3, Na2O).[2] A large number of works et al., in which sulfur is replaced by NiCl2.[5] In discharge, the
were performed to understand the structure and the Na+ diffu- Na+ ions and the electrons react with NiCl2 with formation of
sion process, to optimize the material, and to find new mate- NaCl and Ni metal. Since NiCl2, Ni, and NaCl are solid at the
rials with high ionic conductivity. The structure crystallizes in operating temperature (300 °C) NaCl and AlCl3 are added in
the hexagonal system with two spinel blocks separated by a the positive electrode (Figure 2b). This leads to the formation
mirror plane, which contains one oxygen and one vacancy. This of NaAlCl4, which is a liquid at the operating temperature; the
plane is not compact and contains many empty sites described presence of a liquid facilitates the Na+ conduction on the posi-
by the nomenclature “BR” (Beevers-Ross) and “aBR” (anti- tive electrode. The cell voltage of this cell is 2.6 V instead of
Beevers-Ross) where the Na+ ions are delocalized at high tem- 2.0 V for the NaS cell. The ZEBRA batteries are assembled in
perature leading to a behavior similar to a bidimensional liquid
(Figure 1).[3] Depending on the composition and on the reac-
tion synthesis temperature another structural variety referred
as β″-Al2O3 can be obtained.[4] This material crystallizes in the
rhombohedral system with three spinels blocks separated by
a conduction plane similar to that of the β phase (Figure 1).
Both materials have similar ionic conductivities, which can be
slightly improved by cationic substitution.
The electrolyte was used in the sodium–sulfur battery (NaS)
which was developed by Ford Company for EV in the end of
the 1960s. This battery is made of a β-Al2O3 tube containing
metallic sodium. This tube is inserted in another tube con-
taining liquid sulfur as shown in Figure 2a. The cell oper-
ates at high temperatures (300–350 °C). On discharge sodium
is oxidized, the Na+ ions go through the electrolyte and react
with sulfur, which is reduced with formation of polysulfides.
In practical cells, the ceramics contain a mixture of particles of
β-β″-Al2O3 varieties. Due to the 2D character of the ionic con-
ductivity, research was performed to optimize the particle size
and orientation in the ceramic. One of the main problems of
this technology is the sintering of very dense β-Al2O3 tubes that Figure 1. The sodium diffusion plane in β-Al2O3 and β″-Al2O3.

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led to the discovery of Borate glass ionic conductors and to the

homologous sulfides glasses.[16] In all cases, the ionic conduc-
tivity of lithium-based materials was smaller than that of the
sodium materials. This unexpected behavior, if only the mobile
ion size is considered (Li+ is smaller the Na+), results from the
higher polarizability of sodium. This is a general phenomenon
in ionic diffusivity: e.g., the ionic conductivity in sulfides is
larger than in the homologous oxides.
Simultaneously, at the end of the 1970s, the research groups
of Whittingham,[17] Murphy,[18] Weppner,[19] Huggins,[19] and
Armand[20] opened the way to reversible lithium batteries
with aprotic liquid electrolytes. The very first researches con-
Figure 2. Schematic representation of the sodium/sulfur battery a) and cerned the intercalation of lithium in layered dichacolgenides;
of the ZEBRA battery b). Reproduced with permission.[49] Copyright 2012, TiS2, TaS2, ZrS2, etc.[21–23] The intercalation was done either
Elsevier. electrochemically or chemically (nButyl-lithium). The contri-
bution of Rouxel, who was studying these materials by direct
the discharge state, this make the ZEBRA battery manufac- reaction with alkali metal in solution in liquid ammonia, has
turing safer than the NaS one.[6] to be mentioned.[24] He extended his study to many materials
Following the discovery of β-Al2O3, a significant rush layered chalcogenides.[25,26] At this time, the concept of the
occurred to optimize this material, the cell and to discover new rocking chair battery was known, but the purpose was to make
electrolytes with higher ionic conductivity. All material families lithium metal batteries. Concerning Na battery, only interca-
with tunnels structure (hollandites),[7] layer structures (layer lation in TiS2 and WO3 was considered.[27,28] The researches
oxides and chaclcogenides[8,9] or tunnels structures[10] were move to lithium intercalation in oxides and many of them were
considered. In all of these materials the cations must be dia- tested. In 1982, B. Scrosati organized the first “lithium battery
magnetic to avoid electronic conductivity and not reducible to meeting” in Rome. Eighty researchers attended this meeting.
avoid reaction with the alkali metal (negative electrode). Among This was really the beginning of the Li-ion story.
all the materials which were studied, one has to mention the The layered oxides (LiMO2 and NaMO2 (M = 3d element)
Nasicon (acronym of Na super ionic conductor) which was pro- were all discovered toward the end of the 1960s. The story
posed by Goodenough and Hong for a derivative of the previ- about the sodium deficient phase NaxMO2 started in Bordeaux
ously known NaZr2(PO4)3 phase.[11,12] In this structure there are between 1970 and 1972, when Fouassier published the phase
large interconnected cavities which can be occupied by extra diagram of the NaxMnO2 and NaxCoO2 systems.[29,30] Next the
sodium ions. To increase the number of Na+ charge carriers homologous KxMO2 (M = Cr, Mn, Ni) phases were discovered
they substituted silicates for phosphate groups to obtain the and studied from the structural and physical properties point
Na1+xZr2(PO4)3−x(SiO4)x solid solution.[13] A view of the struc- of views.[31,32] I proposed at this time the structural classifica-
ture is given in Figure 3. Its ionic conductivity is close to that tion which is now currently used.[33] It allows to describe the
of β-Al203 at 200 °C. NaS batteries were built with this electro- structural packing by the combination of a letter (O or P)
lyte, but they cannot exceed the performances of β-Al203-based which denotes the environment of the alkali ions (octahedral
batteries. or prismatic) and a number (1, 2, 3, 4, 6, 9) which identifies the
Then, many studies were devoted to find materials with number of MO2 slabs within the hexagonal cell.
skeleton structures and extended to lithium-based materials In 1978, in Bordeaux, I initiated research on the NaxMO2 lay-
to identify promising Lisicon (lithium super ionic conductor) ered (M = Co, Ni, Cr, Mn, Ti, Nb) oxides with a special focus
type materials like for example Li4−xSi1−xXxO4 (X = P, Al, or on the relationship between electrochemical intercalation and
Ge)[14] or Li4B7O12Cl boracite.[15] These studies on boracites structural modifications.[34–38] In Japan, Takeda studied the
NaxFeO2 system.[39] These studies showed that the shape of the
charge/discharge curves exhibit three main distinct regions;
plateaus, continuous changes in voltage, and voltage drops;
which respectively are characteristic of two phase domains,
solid solutions and single phase compositions with a unique
composition. We also showed the occurrence of reversible slab
gildings leading to change in the surrounding environment
of the sodium ion. From the O3 type observed for the NaMO2
composition, the P3 type structure is obtained upon deinterca-
lation when the amount of sodium is in the range of 0.3–0.5.
The opposite behavior is observed during sodium reintercala-
tion. This behavior is completely reversible. In the case of the
P2-NaxCoO2 phase, we showed that the P2 environment was
maintained even after complete reintercalation. This is due to
the fact that any slab gliding from the P2 packing to from an
Figure 3. The 3D sodium ion pathways in the Nasicon structure. octahedral environment for Na leads to a new packing where

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the NaO6 octahedra share faces with the CoO6 octahedra. The - Simultaneously, concerns about the global abundance of
existence of face sharing makes the material very unstable lithium have grown due to the rapid increase of battery
and therefore this structural change does not occur in sodium production and the emergence of electrical vehicles, which
systems upon Na reintercalation. That remark led to the syn- require large high capacity batteries. The rapid development
thesis of a new variety of O2-LiCoO2 by Li+/Na+ exchange from of renewable energy systems, which have specific require-
P2-NaxCoO2.[40] This was the first report on this structural type. ments, contributes also as researchers try to explore new
During our study of Nasicon type solid electrolyte, we syn- fields with elements other than lithium. Three elements
thesized the Na3M2(PO4)3 (M = Ti, V, Cr Fe) phases,[41] which have been primarily considered: Na, Mg, and Al.
were potential electrode materials in the reduced state. This led
in 1987 to the first Na(Li) battery with a phosphate as positive In the case of Mg and Al batteries, the argument was to use
electrode material. We intercalated Na in NaTi2(PO4)3 electro- multivalent cations to increase the specific energy. I do not
chemically and chemically.[42] We obtained the same behavior know if it was a dream or a lure. To increase the capacity one
in the lithium homologous system. At this time, it was gener- has to increase the number of electron transferred in the elec-
ally admitted that the low electronic conductivity of phosphate trode for a given mass. It is not the charge of the intercalated
materials was a drawback to obtain good electrode materials; ion which is the key point, but the change in the oxidation state
particularly in the Nasicon type structure where the TiO6 of the active ion in the electrode.
octahedra do not share any oxygen atoms (Figure 3). The elec- Many laboratories shifted their research focus to sodium
tronic transfer involves Ti-O-P-O-Ti bonds. Nevertheless, our materials. This was an easy path because most of the struc-
magnetic study of the Na3M2(PO4)3 (M = Ti, V, Cr, Fe) phases tures of lithium and sodium materials are very similar, the syn-
showed the presence of antiferromagnetic ordering below thesis routes are very well described. As a result, in 5 years, the
50 K that demonstrated the occurrence of electronic interac- number of papers was multiplied fivefold (Figure 4). It is not
tions through the PO4 tetrahedra.[43] the purpose of this article to present detailed results. This is
In 1989, Sony commercialized the Li-ion battery with a done in all of the following chapters. Many general reviews are
carbon negative electrode thanks to the contribution of Yoshino reported.[48–55] Only general points concerning the most impor-
from Asahi Kasei.[44] This technology, which allows long range tant materials families will be given here.
cycling and avoid the dendrite formation, opened the way to
use lithium-ion in all devices. Thereafter, almost all researches
in the world were focused on lithium materials and related 3.1. Positive Electrode Materials
systems.
At the end of the twentieth century, Dahn studied the layered 3.1.1. Na Layered Oxides
Nax(Mn,Ni)O2 materials as precursors to obtain new lithium
materials by (Li+/Na+) exchange and also as positive electrodes Na layered oxides were the most studied in the past, as pre-
for Na-batteries.[45,46] He discovered the interesting proper- viously described, and then again as a first step, when all
ties of hard carbon as sodium anode materials.[47] During the these materials were revisited, since the current characteriza-
2000–2008 period published research on Na batteries material tion methods are more advanced than 30 years ago. Three
was slowly increasing, mainly done in the few labs in the world types of Na layered oxide structures can be obtained by high
which have historical expertize in this field.

3. The Sodium Renaissance

Suddenly, in 2008 the number of papers related to Na-batteries
increased very rapidly as many new labs became involved in
this topic. There are several explanations for this change:

- In the lithium battery domain most of the researches con-

cerned Li–air and Li–S batteries, Si negatives electrodes, and
Li-rich phases. Almost all known materials, which seemed
potentially interesting as electrode materials, were tested.
While it is quite easy to study the electrochemical proper-
ties of a known material, one only needs to reproduce the
synthesis and make a battery; it is more complicated to dis-
cover new material families. Finding new materials requires
several years of experiments and a strong expertize in solid
state chemistry or exceptional luck. The research is always
intensive in these fields, but it is mainly focused on work to
improve the known materials for applications and to under-
stand the fundamental mechanisms involved in the electro- Figure 4. Comparative evolution of the number of publications per year
chemical process. for lithium and sodium batteries.

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particularly interesting.[74–76] A new mate-

rial family, Alluaudite, was used as elec-
trode by Trad[77] and then studied in detail
by Yamada.[78] The pyrophosphate materials,
which were proposed for the first time by
Okada and Yamaki,[79] were also considered
by Yamada.[80] The studies were extended to
mix phosphate and pyrophosphate.[81]
Concerning fluorophosphates, the pio-
neering contributions of Barker[82] has
to be mentioned which was the origin of
several interesting materials exhibiting
very good performance (NaVPO4F[83] and
Na3V2(PO4)2F3.[84] Croguennec, Masquelier
and Carlier demonstrated the occur-
rence of F–O mixing in the structure of
Na3V2(PO4)2(F,O)3.[85] Nazar proposed
Na2FePO4F which can be used as positive
electrode or as precursor for the homologous
lithium phase.[86] Tarascon proposed sodium
Figure 5. Structures of the O3, P3, and P2 layered oxides. The sodium environment is repre-
fluorosulfates.[87,88] The presence of sulfates
sented for each structure.
increases the cell voltage versus phosphates.

temperature chemistry and used as electrode materials (gener-

ally as positive electrodes) (Figure 5). 3.1.3. Miscellaneous
At the beginning, researches were focused on layered
materials with only one transition element. One can note Interesting results were obtained from Prussian Blue type
the work of Komaba who contributes to the renewal of these phase which were proposed for the first time present by
researches.[56,57] Ceder also make interesting studies experi- Imanishi[89] for lithium batteries and by Goodenough for Na
mentally and by density functional theory (DFT).[58,59] In our batteries.[90] Their structure can be considered as perovskite
lab we determined in details the phase diagram of complex derivatives with CN instead of oxygen.
systems by in situ XRD diffraction of NaxMO2 materials (M = As proposed by Armand,[91] who is the pioneer in the field
Co, V, Mo).[60–62] The profile curves of NaxMO2 (M: a single ele- of organic materials as electrode materials, organic batteries
ment present) show evidence for the occurrence of several pla- are very promising (high capacity and energy density, but low
teaus and voltage drops due to Na- vacancy ordering or slab power). Recently, interesting results were obtained by Okada[92]
gliding in the case of the O3 type phase. In order to prevent on Na2C6O6 and by Chen on Na4C8H2O6.[93] This last material
the ordering and to improve the electrochemical performances can be used as positive and negative electrode material leading
the researches moved toward more complicated materials with to a rocking chair battery. Nevertheless, in this electrode con-
several cations (up to four) in the MO2 slab. Yabuuchi and figuration de capacity is strongly decreased. The activity in this
Komaba proposed in 2102 the P2-Nax(Fe,Mn)O2 system, which field has to be increased.
is one of the most promising one considering the cost and the
material availability.[63] Mortemard de Boisse,[64] Obrovac,[65]
Nazar,[66] and Rojo[67] contributed strongly to the researches 3.2. Negative Electrode Materials
on this material family. Several hundred papers were devoted
to mixed materials with no significant improvement in perfor- The requirements for negatives electrodes materials are very
mance. In addition to the authors previously mentioned, we similar to those of positive electrodes. The main difference
must not forget the contributions of Passerini,[68] Meng,[69] Grey concerns the voltage requirements which must be low voltage
and Clement,[70] who performed very fundamental studies to versus Na+/Na couple, but not too similar in order to impede
understand the involved mechanisms. any dendrite formation. Studies of these materials are made, as
for the positives electrodes, in half-cells versus sodium metal as
negative electrode. In this case, in order to be used in practical
3.1.2. 3D Polyanions Oxides cell as negative electrode, it is the charge (Na deintercalation
curve of the half-cell) which must be considered and not the
Following the intercalation of sodium in NaTi2(PO4)3[42] and discharge. In most of the papers, it is the discharge capacity
the interest in LiFePO4 discovered by Goodenough, studies which is considered instead of the charge. Only the capacity in
on 3D skeleton structures became very popular.[71] In 2013, charge below 1 V of the half-cell must be taken into account
Masquelier and Croguennec made a very detailed review of to determine the realistic capacity. If this charge voltage is too
materials with polyanions structures as electrode materials.[72] high, this will lead to a practical full-cell with very low voltage.
The Nasicon type phase Na3V2(PO4)3[73] and NaFePO4 are The same tendency is observed in the case of lithium batteries.

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oxygen. Its use in a practical cell cannot be considered. The

same difficulty occurs with all metallic phosphides. Ni3P,
reported by Monconduit, reacts electrochemically with up to six
sodium atoms, in a reversible way, with formation of Na3P in
discharge.[103]
Organic materials are also considered for the negative elec-
trode.[104] Like for previous materials most of them present a
large irreversible capacity and require a high voltage for deso-
diation, which impedes practical uses in full Na-ion cells. In
the case of Na2C8H4O4 a reversible capacity of 200 mA h g−1 in
Figure 6. “House of cards” model for sodium/lithium filled hard
carbon. Reproduced with permission.[47] Copyright 2000, Electrochemical obtained at 0.5 V versus Na+/Na.[105] Unfortunately, this mate-
Society. rial also presents very high irreversible capacity.

Most of the negative lithium materials working with a conver-

sion reaction require high voltage (vs Li) to be deintercalated: 3.3. Na–Air
this means that they have no real practical interest. In the
following, only the material corresponding to these criteria will Sodium–air batteries are also particularly interesting. Janek
be considered. succeeded to make a cell with a high capacity and a low polari-
Like for lithium batteries, the carbonaceous materials zation in comparison to what it was observed in the Li–air bat-
presently are the most interesting. It is well known for more teries.[106] Following these results, many labs were involved
than 50 years that sodium cannot be intercalated within in this topic.[107–109] It should be noted the contribution of
graphite to a significant extent. Doeff succeeded to insert Zhang who made an efficient cathode for Na–O2 batteries by
reversibly sodium in soft carbon obtained by pyrolysis of petro- using a nitrogen doped carbon with a hierarchically porous
leum coke.[94] In 2003, Dahn reported the intercalation in hard structure.[110]
carbon obtained by carbonization of glucose and proposed a
structural model called “house of cards.” Sodium is inserted
simultaneously between the graphene layers and nanopores 4. Conclusion and Perspective
present in this disordered material (Figure 6).[47,95] The revers-
ibility of the reaction is very good and the capacity is on the Research on Na-ion battery materials has strongly increased
order of 300 mA h g−1. More recently this reaction was revisited during the last 10 years and is now competitive with that on
by Kubota and Komaba who succeeded to improve the cycling Li-ion battery materials. All studies carried out on lithium sys-
properties by using high purity salt and electrolyte, FEC as tems were successfully transposed to Na materials and most of
additive and optimized binders.[52] Recent studies are summa- the mechanisms discovered to explain the Li systems can be
rized in several reviews on carbonaceous materials.[96,97] applied to the case of Na, even if some of them are different. In
Titanium oxides are well known for their alkali metal inter- most cases, the electrochemical behavior of Na phases is more
calation at low voltage thanks to the reductive character of Ti3+. complicated than that of Li phases. The large size of sodium
Among all studied titanium derivatives, only Na2Ti3O7, which versus lithium increases the steric interactions and tends to
was proposed by Palacin, seems interesting but cannot compete increase the occurrence of cation ordering. The ionic conduc-
with hard carbon.[98] In the case of the P2-Nax(Li,Ti)O2 layered tivity of Na+ ion is similar and even larger than Li+ due to its
oxide, Li and Huang succeeded to intercalate sodium below 1 V polarizability.
(100 mA h g−1).[99] This material was used as negative electrode Because of the difference in redox potential between Li and
of a full cell with Na3V2(PO4)3 as positive electrode.[99] Na, the cell voltage of sodium cell is smaller (0.3 V) than in the
Some alloys have interesting electrochemical properties. One case of lithium half-cells. This effect must disappear in the case
of the main problems of alloys is the volume change, which of full cells. Depending on the involved systems there are no
occurs during the sodium intercalation and leads to significant defined rules. It depends on the difference in energy between
fading. In the case of tin metal alloys, almost 4 Na atoms can be positive and negative intercalation compounds. In the case of
inserted in tin (Na15Sn4) leading to a capacity of 500 mA h g−1 layered materials, there is a large energy difference between
below 1 V. The strong increase in volume (420%) requires the LixMO2 and NaxMO2 phases leading to a significant lower
limits on the capacity exchanged and requires material optimi- voltage for sodium cell. Most of the Na-based systems have a
zation by making composites to decrease the constraints.[100] lower specific and volumetric energy lower that their lithium
Sb and Sb-based alloys are also candidates as sodium nega- equivalents due to the difference in atomics weight and ionic
tive electrodes. Up to three Na can be inserted in the Sb lattice radii (Figure 7).[70]
with formation of an amorphous phase.[101] Nevertheless, Sb Over the past years, most of the researches have been focused
is a quite rare element and its use in large cells for renewable on the discovery of new materials. While new compounds still
energy seems unlikely. have to be synthesized, it is also important to increase focus on
Phosphorous was also proposed as it presents very good battery optimization incorporating the best performing known
electrochemical properties.[102]Nevertheless, Na3P reacts spon- materials. Only few prototypes, using hard carbon as negative
taneously with water to form phosphine (PH3) which a very electrode, have been reported. The first battery, with a multiele-
dangerous toxic gas and burns spontaneously in presence of ment layer oxide as positive electrode, was made by Faradion for

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Most of the studies concern Na-ion bat-

teries with a liquid electrolyte. Nevertheless,
like for lithium systems, for safety issues
solid state batteries have to be considered in
the future. The challenge is to find a highly
conductive solid electrolyte with a large elec-
trochemical window. In 2012, Hayashi et
al. reported an Na3PS4 glass-ceramic with a
high ionic conductivity (0.2 mS cm−1).[116]
Following this discovery, efforts were made
to improve the conductivity (pseudo binary
system Na3PS4–Na4SiS4 or Cl doping).[117,118]
All solid state Na batteries were made with
TiS2 as positive electrode.[118]
Ultimately, the choice of the best active
material will depend on the applications.
For the case of stationary batteries, it is the
price and the availability that are the key
points. If they gain widespread use for smart
grid frequency regulation, linked to renew-
Figure 7. Average discharge potential (V vs Na+/Na or vs Li+/Li for the blue and yellow hexa- able energy and short time storage for peak
gons, respectively) and volumetric energy density (W h L−1) versus volumetric capacity (A h L−1) shifts, the number of these large batteries
for selected positive electrode materials for NIBs and LIBs. Reproduced with permission.[70] in the world will be enormous. Then only
Copyright 2015, ECS. very abundant elements must be considered;
most of the materials discussed in this book
an electric bike.[111] 18 650 type cells were made by the Réseau do not satisfy this requirement.
Stockage Electrochimique Energie (RS2E)-Centre National Nevertheless, the science is a unique world; the fundamental
Recherche Scientifique (CNRS)-Commissariat Energie Atom- researches made even on very exotic systems help to optimize
ique (CEA) network. These cells, with Na3V2(PO4)2F3 as positive the applied materials. Over the last 40 years, the characteriza-
electrode material, exhibit a specify energy of 90 W h kg and a tion techniques have been improved in a fantastic way. Using
good cyclability (3000 cycles).[112] Recently, Mitsubishi Corpo- DFT calculations one can simulate and predict the behavior of
ration obtained very promising results with a nongraphitizable a compound. Now, we are able to see the atomic columns. We
carbon and the P2-Na2/3(Ni1/3Mn2/3)O2 phase as electrode mate- have not to imagine what is going on, we have the picture in
rials.[113] The journey from the lab to the factory is always dif- front of us. Nobody can predict the progress of science in the
ficult and requires considerable effort and investment. next 20 years.
Only the active materials were considered here; but now, Politicians, government agencies, and companies are mainly
all other components of the battery also have to be optimized; concerned by applications. We have to convince them that all
the electrolyte (solvent and salt), the binders, the additives to discoveries, which have changed our world, come from fun-
manage the SEI formation. As clearly shown by Kubota and damental researches. Sometimes one of us makes a great dis-
Komaba in their review paper,[52] the optimization of the elec- covery, but in fact, his scientific culture was fed by the work
trolyte (salt and solvent) is a very complicated problem and made by all other researchers.
must be realized for the full cells. Moreover, generally the sol-
vent is a mixture of several compounds that have specific prop-
erties versus the electrode material and the cell voltage. As in Conflict of Interest
the real full cell the amount of electrolyte is limited, the role of
The authors declare no conflict of interest.
the products formed thanks to the degradation of the electrolyte
must be also considered. The purity of the solvent and of the
salt plays an essential role.
The behavior of the interfaces must be intensively studied.
Keywords
All these properties are specific for each electrode material, electrode materials, sodium batteries, sodium-ion batteries
which have all peculiar electrocatalytic activities. Not only the
Received: November 9, 2017
chemical formula of the electrode material is concerned by
Revised: December 14, 2017
this point; the size of the particle and the local structures of Published online:
the surface plane play a very important role for the reactivity
problems. These studies must be realized using the various
electrode materials, which are most promising for future appli-
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