Phil. Trans. R. Soc.

A (2010) 368, 3227–3241

doi:10.1098/rsta.2010.0112

REVIEW

Key challenges in future Li-battery research

B Y J.-M. T ARASCON1,2, *
1 Laboratoirede Réactivité et Chimie des Solides, Université de
Picardie Jules Verne, CNRS (UMR-6007 ), 33 rue Saint-Leu,
80039 Amiens, France
2 ALISTORE-ERI European Research Institute

Batteries are a major technological challenge in this new century as they are a key
method to make more efficient use of energy. Although today’s Li-ion technology has
conquered the portable electronic markets and is still improving, it falls short of meeting
the demands dictated by the powering of both hybrid electric vehicles and electric vehicles
or by the storage of renewable energies (wind, solar). There is room for optimism as
long as we pursue paradigm shifts while keeping in mind the concept of materials
sustainability. Some of these concepts, relying on new ways to prepare electrode materials
via eco-efficient processes, on the use of organic rather than inorganic materials or
new chemistries will be discussed. Achieving these concepts will require the inputs of
multiple disciplines.
Keywords: cells, batteries; energy

1. Introduction

Energy is the lifeblood of modern society. Global warming, finite fossil-fuel

supplies and city pollution conspire to make the use of renewable energy, together
with electric transportation, a worldwide imperative. There is a pressing need
to design electrical-energy-storage systems to balance supply with demands,
as renewable sources are intermittent, and to power the upcoming plug-in
hybrid electric vehicles (PHEVs) or electric vehicles (EVs). Numerous energy-
storage solutions enlisting mechanical, magnetic, chemical storage, etc., are being
presently investigated. Therefore, as we want to store energy in order to restore
it as electricity, the most attractive path is to convert chemical energy into
electrical energy, as they both share a common carrier, namely the electron.
Fuel cells and batteries are electrochemical storage devices that ensure such
conversions to occur in a single or reversible way, respectively. As fuel cells are
frequently referred to as an emerging technology, in spite of 200 years of research,
we have focused this paper on batteries since they are the main contenders
to better manage the renewable resources of our planet, and to favour the
*jean-marie.tarascon@sc.u-picardie.fr

One contribution of 13 to a Discussion Meeting Issue ‘Energy materials to combat climate change’.

3227 This journal is © 2010 The Royal Society

3228 J.-M. Tarascon

deployment of electric cars so as to limit pollution. It should indeed be recalled

that each time we burn 1 litre of gasoline, we are liberating 1.5 kg (e.g. 750 l)
of CO2 .
Among present battery technologies, Li-ion technology is the best
performing one owing to its delivered energy density (210 Wh kg−1 ; 650 Wh l−1 ),
which exceeds any competing technologies by at least a factor of 2.5
(Tarascon & Armand 2001). With such attractive performances, coupled with its
long life cycle and rate capability, Li-ion technology has captured the portable
electronic market, invaded the power tool equipment market, previously kept
for Ni–MH technology, and is on the verge of penetrating the EV market on
condition that improvements can be achieved in terms of cost and safety. Indeed,
long-term stability, high-energy density, safety and low cost seem to be the over-
riding factors in high-volume applications. Therefore, it implies assessing present
Li-ion technology so as to define the challenges that lie ahead to ensure its long-
lasting success (Armand & Tarascon 2008). Attempts to answer such questions
will constitute the core of this paper, which will mainly, but not exclusively,
deal with Li-ion technology. Research directions to increase the Li-ion battery
energy density, lower its cost, improve its safety and make it more sustainable
and ‘greener’ will be discussed. New upcoming chemistries will also be brought
to the scene and benchmarked with today’s systems.

(a) Means to increase energy density

Despite the new lease of life recently brought by the arrival of nanomaterials,
present Li-ion technology falls short of meeting all of the requirements dictated
by the large volume of applications linked to renewable energy and electric
transportation fields. First, we should be aware that a colossal task is awaiting
us if we really want to compete with gasoline, as an increase by a factor of 15
is needed for the energy delivered by a battery (180 Wh kg−1 ) to match the one
of a litre of gasoline (3000 Wh l−1 ; taking into account corrections from Carnot’s
principle). Knowing that the energy density of batteries has only increased by a
factor of five over the last two centuries, our chances to have a 10-fold increase
over the next few years are very slim, with the exception of unexpected research
breakthroughs. Fortunately, the automotive industry has set a more realistic
target: doubling the present Li-ion energy density in the next 10 years so that
the autonomy of EVs approaches 500 km. The energy density of a battery is
the product of its capacity and its potential, and is mainly governed by the
capacity of the positive electrode. Simple calculations show that an increase in
cell energy density of 57 per cent can be achieved by doubling the capacity of
the positive electrode, while one needs to increase the capacity of the negative
electrode by a factor of 10 to get an overall cell energy density increase of 47
per cent (Tarascon 2002). So, the chances of drastically improving today’s Li-
ion cells energy density are mainly rooted in spotting better positive electrode
materials, i.e. materials that could either display greater redox potentials (e.g.
highly oxidizing) or larger capacity (materials capable of reversibly inserting more
than one electron per 3d metal).
Knowing that the redox potential of an intercalation compound mainly tracks
the iono-covalency of the metal–X bonding, fluorine (F) substitution appears to
be quite an attractive direction to increase the material redox voltage (V), as F

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3229

active material:
(a) 10nm
nm
10 electronic insulator
electronic

current collector
conducting phase

interphase adhesion
via van der Waal forces,
chemical bonding

pores: space for

liquid electrolyte

(b) (d) active porous skeleton with

thin walls between pores
10 nm
(c)
liquid

current collector
electrolyte
electrolyte Li+ +
Li
conductive
carbon Li+ Li+

active conductive film on Li-based electrolyte

electron- particles within the pores
walls of pores
conducting
molecules
mixed conducting
matrix

Figure 1. Schematic of a perfectly wired electrode (a) with variable options to be pursued given
from left to right as follows: (b) the molecular bridging, (c) the mixed ion conducting and (d)
the reverse-structuring approaches, which each have their merits and pitfalls as discussed in the
text (courtesy of G. Amatucci and M. Gaberscek).

is very electronegative. Therefore, a drawback brought about by F substitution

concerns materials having large band gaps (e.g. poor electronic conductivity),
which usually display poor ionic conductivity when containing Li. As the latter is
an intrinsic value, there is a need to synthesize these materials at the nanoscale,
as the intercalation time (e.g. the time for Li ions to move from the core to
the particle surface) decreases with the square root of the particle size. These
nanoparticles must additionally be carbon coated if one ever wants these F-based
materials to be competitive in terms of power-rating capabilities. Apart from
fuelling electrons through the entire electrodes, carbon coatings, which stand
as a buffer layer between the active material and the electrolyte, also help in
minimizing electrolyte degradation; the latter is usually quite important, with
highly oxidizing electrode materials functioning at potentials well beyond the
thermodynamic potential of the electrolyte (Simon & Tarascon 2009).
Another approach towards increasing energy density consists of identifying
materials that could reversibly accept more than one electron per 3d metal. At
first sight, Li2 MnSiO4 appears quite attractive, as the presence of Mn+2 could
imply the feasibility of removing two lithium atoms (Mn2+ → Mn+4 + 2e− ). So
far, experimental attempts (Gong et al. 2006) have remained unsuccessful in
accordance with theoretical calculations (Gaberscek et al. 2007; Kokalj et al.
2007), which indicate the non-thermodynamic stability of the fully delithiated
MnSiO4 phase. This further confirms the difficulty in spotting compounds that

Phil. Trans. R. Soc. A (2010)

3230 J.-M. Tarascon

could reversibly react with lithium via an insertion/de-insertion process involving

more than one Li+ per 3d metal. This contrasts with conversion reactions that can
enlist, according to the overall reaction (Mn Xy + . . .), the reversible uptake of two
(CoO) (Poizot et al. 2000) to six Li+ (NiP2 ) (Gillot et al. 2005) per 3d transition
metal at potentials that depend on the iconicity of the M–X bond, with the
highest redox potential for the highest electronegative anion (e.g. F−). However,
the main drawback in the conversion of positive electrodes (FeF3 ) lies both in their
high polarization and in the absence of Li in their initial stage, so that they can
only be used in Li rather than Li-ion cells. To eschew the latter, there is always the
feasibility of making (MX–LiX) composites via ball-milling, which can be used
as a Li reservoir and be stable in a moisture environment if the conversion redox
potential exceeds 3.2 V (Amatucci & Pereira 2007) burning 1 litre. In contrast,
chances of lowering the polarization for conversion electrodes remain slim since
we have shown that this polarization is linked to the iconicity of the M–X bond
and its redox potential, both increasing with compounds showing a high ionic
character (fluorides) and decreasing with highly covalent compounds (hydrides)
(Oumellal et al. 2008). However, owing to the staggering capacity gain that such
electrodes provide, they should continue to be a high-topic research, even though
the remaining task of increasing their energy efficiency is not perceived as an
easy one.
Interestingly, most of the new paths mentioned to increase energy density
result in the use of materials whose both electronic and ionic properties are very
poor; therefore, the need to grow highly divided materials in order to decrease
the Li-ion transfer path for Li uptake/removal is a must, as well as the use of
conductive coatings for providing electrons throughout the entire electrode (Arico
et al. 2005). Carbon coatings combined with particle-size reduction have been
successfully used to trigger the electroactivity of LiFePO4 (Ravet et al. 1999).
Although quite useful, such an approach cannot be used for highly oxidizing
compounds such as LiCoO2 and LiFePO4 F, for instance, because of the reducing
nature of the carbon treatment, which results in decomposition of the treated
material; hence, the need to find alternatives to improve electrode kinetics
(Gaberscek et al. 2005; Gaberscek & Jamnik 2006). With all the limitations
that such a comparison could bear, an electrode material can be visualized as
our brain, where all the neurones (in our case active nanoparticles) must be
electronically and ionically nicely wired to ensure proper functioning. Mindful
of these considerations, several approaches, most of which consist of controlling
electrode architecture at the nanolevel, have been pursued (figure 1). They enlist
the design of electrodes based on molecular bridging via the coating of particles
with electron-conducting polymers such as polyethylene di-oxyethylene thiphene
(PEDOT; Meng et al. 2003; Shen & Lee 2005), or the grafting of a molecular
conductor redox relay (e.g. 3.5 V versus Li/Li+ ) such as triaryl amine substituted
for a benzyl phosphonate group, as recently demonstrated by Greatzel’s group
on LiFePO4 (Wang et al. 2007). Parallel approaches consisting of (i) preparing
highly mixed solid conductor composites (e.g. CuF2 –MoO3 ), as demonstrated
by Amatucci’s group (Badway et al. 2007) and (ii) growing ordered mesoporous
materials (Bruce et al. 2008), consisting of micrometre-sized particles, within
which pores of 2–5 nm do exist to host the electrolyte, have been successfully
made. For such concepts to fully reach fruition, there are some remaining
challenges. While the approach referred to as either inverse structuring, replica or

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3231

chemical templating, has been successful in preparing numerous binary phases,

it has been solely limited to LiMn2 O4 for Li-bearing positive electrodes (Bruce
et al. 2008). Hence the need to grow ordered mesoporous Li-bearing positive
electrodes if one wants such a new class of poorly conducting electrodes (silicates,
phosphates and fluorophosphates) to be efficiently implemented in Li-ion cells.
Additionally, further studies must focus on the molecular-bridging approach, with
the need to (i) design, on demand of molecular layer, relays having a redox
potential closely matching that of the insertion material, (ii) search for electron-
conducting polymers beyond PEDOT, together with better chemical means
to ensure a uniform coating, and (iii) identify mixed ion/electron-conducting
polymers. Although this last task may appear tremendous, the pay-off could
be huge, as mastering electrode wiring is keen in the optimum functioning of
electrochemical storage devices, regardless of what they are (supercapacitors,
batteries, fuel cells, etc.).

(b) Means of increasing safety

Manipulating energy inevitably leads to intrinsic safety risks that hold
regardless of the devices or electrochemical systems used, with the rule of
thumb being that the risks increase with the size of the energy-storing device;
hence the requirement for extra safety conditions for large-sized batteries in the
case of PHEV and EV applications. Numerous attractive solutions relying on
either the use of chemical additives to the battery electrolyte (solid–electrolyte
interface (SEI) modifiers, shut-down and redox shuttles additives, ionic liquids)
or improved cell design and electronics have been pursued, as shown in figure 2;
therefore, Li-ion technology is not exempt from incidents. More conservative
approaches (Ariyoshi & Ohzuku 2007) consist of coupling a highly oxidizing
positive electrode material (LiMn2 O4 or others) with a less reducing material
(Li4 Ti5 O12 instead of carbon) in order to eliminate the formation of a solid
electrolyte interface at the negative electrode, which is a source of concern when
dealing with safety. Therefore, this approach provides extra safety at the expense
of the battery performance, as LiMn2 O4 /Li4 Ti5 O12 Li-ion cells display a low
energy density of 85 Wh kg−1 when compared with 140 Wh kg−1 for LiMn2 O4 /C
cells (Amezutsumi et al. 2007). Overall, it turns out that whatever the followed
approach might be, safety and cost follow each other. Along that line, it is
unfortunate that, today, the Li-ion battery is the victim of fierce cost cutting
and attempts to cram more and more energy in the same volume; therefore,
there is a constant risk of safety issues.
Besides accepting this cost–safety tie, future Li-ion technology will
undoubtedly rely on a sound understanding of electrode–electrolyte components,
especially as we move to the next generation of either positive electrodes based on
higher voltage (5 V) insertion nanomaterials or negative non-insertion electrodes
(e.g. Li-alloying or conversion reactions) made of highly divided materials. Novel
strategies to harmoniously couple the next generation of cathodes or anodes
with suitable electrolytes will have to be found. Future research necessitates to
challenge past basic understanding of electrode–electrolyte interfaces, designing
new cell components (electrodes, electrolytes, additives), and also setting up new
experimental protocols to better analyse the electrolyte degradation products in
either a passive (in situ) or active (post-mortem) way.

Phil. Trans. R. Soc. A (2010)

3232 J.-M. Tarascon

LiFePO4 LiCoO2
zero
risk 2–3 V 5V
improved safety
2 V LiFePO4/ through chemistry
LiBOB/ improved safety
redox via cell
Li4Ti5O12
Wh

electrolyte shuttles design and

additives
electronics
coatings
shut-down dry
additives pressure limiting
polymers
shut-down ionic valve
SEI separators liquids power temperature
modifiers control switch *solid-state
materials thermal Li-ion batteries
chemistry management
inorganic
battery-monitoring materials
system
kWh

safety
battery-management
system cost

Figure 2. Safety aspects in Li batteries. The various chemical and engineering/devices approaches
aimed towards increasing Li-ion battery safety are mentioned. Distinction is made as a function of
both (i) the type of applications considered (y-axis) and (ii) the type of redox chemistry involved
(x-axis). Designing low-voltage systems, Li4 Ti5 O1 2/LiFePO4 , increases safety at the expense of
cost, conveying the general message that changes in safety and cost always track each other. While
long far-reaching, the development of solid-state batteries is mentioned as the ultimate solution to
reach zero risk. (Adapted from ALISTORE-ERI white paper on safety; M. Armand, P. G. Bruce,
L. Croguennec, M. Morcrette & J.-M. Tarascon 2008, internal communication.)

The use of solid-state Li-ion batteries based on either dry polymer or inorganic
electrolytes can be seen as the ideal solution. More than 30 years of research has
already taken place in this research field, but several hurdles do still remain.
For such an idealistic situation to come through, drastic improvements and
breakthroughs must occur so as to increase the electrolyte conductivity. With
the present renewed interest in both room- and high-temperature solid-state
batteries, together with the new records achieved in glass-ceramic conductivities
(10−3 S cm−2 ) within the Li2 S–P2 S5 system (Minami et al. 2007), or LiBH4 –
LiI (Maekawa et al. 2009), together with new electrode-assembly techniques,
optimism must prevail. Within the field of dry-polymer research, our challenge
nowadays is to end 30 years of frustration with an approach to design better
ion-conducting polymers to enable the 25◦ C operating temperature. A colossal
amount of work went into the exercise of loading polymeric matrices with nano-
inorganic fillers (Croce et al. 1998); but, the results still fall short of meeting
expectations. Aware of the positive attributes of nanostructuration to the cell
electrode components, time has certainly come to implement the same concepts
to the design of future polymer electrolytes. Although the nanostructuration of
polymers has remained rather neglected, it is believed that approaches relying

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3233

ceramic
solvothermal
process hydrothermal
process ionothermal
process
process biomineralization
process

lower temperatures economy of atoms

TFSI –
bulk N N
nano

Figure 3. Towards energy and materials thrift for LiFePO4 preparation. Numerous methods
enabling both a lowering of the synthesis temperature and the formation of highly divided powders.
While ceramic, hydrothermal and solvothermal approaches are well established, the ionothermal
synthesis approach is totally new. The biomineralization approaches are well known, but their
in-road within the field of electrode materials synthesis is just appearing (Tarascon et al. 2010).

on nanophase separation in block copolymers or self-organization of polar and

non-polar bloc copolymers at the nanoscale could have a bright future based on
the design of high ion-conducting polymer membranes.

(c) Means of reducing costs

There are numerous means of enlisting both engineering (cell manufacturing
and assembly) and chemical (materials design and electrode composition) factors
to combat the exceedingly high cost of the Li-ion technology, which nowadays
ranges from 800 to 300 $ kWh−1 , as opposed to about 50–100 $ kWh−1 for lead-
acid technology. At the material level, which is the focus of the paper, the cost
is mainly dependent upon the material-synthesis process, its abundance and
renewability. This is the reason why materials based on sustainable 3d metal
redox elements such as Mn (LiMn2 O4 ), Fe (LiFePO4 , Li2 FeSiO4 ) and even Ti
(TiO2 , Li4 Ti5 O12 ), and made via eco-efficient processes, are receiving increased
interest with respect to Co or Ni-based electrodes relying on limited elements, and
which are usually made at high temperatures. Nevertheless, although LiFePO4 is
a mineral known as ‘triphylite’ in nature, it cannot be used directly as such owing
to its poor conducting properties. Synthetic triphylite has to be made aiming at
grain sizes that can be directly processed looking for the most expeditious and
energy-saving processes (Recham et al. 2009a,b).
Aware of this conjuncture, chemists have greatly explored, over the last few
years, new eco-efficient ways to process electrode materials (figure 3) by first
revisiting classical hydrothermal (Chen et al. 2007)/solvothermal (Delacourt et al.
2006) synthesis paths, which mainly consist of reacting in water metal–non-
metal-based soluble salts with a base, and increasing the temperature to promote
the growth of the desired phase via Ostwald ripening. Besides the feasibility
of proceeding at low temperatures (e.g. low energy demand) and in a water

Phil. Trans. R. Soc. A (2010)

3234 J.-M. Tarascon

medium (e.g. green solvent), such processes enable, via fine-tune control of
the reaction pH, the concentration of the precursors, with the preparation of
homodisperse powders having a well-defined shape and size. It contrasts with
ceramic methods, which require high temperatures (e.g. high energy demand) to
ensure the diffusion of the reactants and the growth of the grains, usually leading
to highly polydisperse powders.
Other innovations brought back by revisiting low-temperature-synthesis
methods enlist (i) the appearance of microwave-assisted solvothermal processes
(Theivanayagam et al. 2008) that shorten reaction times and therefore stand
as an attractive high-throughput synthesis method and (ii) the implementation
of ionothermal synthesis to the field of inorganics with very appealing results
(Recham et al. 2009a,b). Like water, ionic liquids provide a highly solvating and
reacting medium while showing no volatility, so that the use of cumbersome
autoclaves, needed when operating in water, is no longer necessary. Moreover,
owing to the flexible chemical design of cationic–anionic pairs, they present,
as solvents, great opportunities for purposely directing nucleation (Recham
et al. 2009a,b). Using ionothermal synthesis, nanopowders of numerous known
electrode materials (Recham et al. 2009a,b) were made in glass vessels at
temperatures below 250◦ C, while temperatures greater than 600◦ C were necessary
to make heterodisperse powders by the ceramic process. Ionic liquids are definitely
costly; therefore, their initial cost is deemed by the fact that they can be recycled
several times without any need for purification when preparing several batches
of the same materials. This newly developed synthesis method is rapidly getting
recognized worldwide by numerous groups. It offers great opportunities towards
the stabilization of new materials and, as a high-throughput synthesis method,
to rapidly map ternary phase diagrams. Therefore, it still requires some energy,
as temperatures of 200–280◦ C are usually required.
When scientists have to find extreme eco-efficient synthesis processes, they
often turn to life chemistry, which is rich with virtually unlimited and incredible
reaction mechanisms. For more than millions of years, micro-organisms have
learnt how to make nanostructured materials or hierarchical porous structures
under ambient conditions. Mindful of these considerations, bioinspired or
biomimetic approaches towards material sustainability and renewability issues are
appealing, and we are witnessing increasing numbers of studies in the biomimetic
field of electrode materials for Li-ion batteries (Tarascon 2008). Biologically
induced mineralization via the use of a bacterium by the name of ‘Bacillus
pasteurii’ has long been reported for calcite precipitation (Wang et al. 1999;
Sondi & Matijevic 2001). Using the same bacterium to provoke the hydrolysis of
urea and generate a basic medium, we recently witnessed some evidence for the
possible growth of LiFePO4 nanofilaments at temperatures as low as 65◦ C (F.
Guyot, N. Reham & J. M. Tarascon 2008, unpublished results). As spectacular,
although not yet practical, is Belcher’s recent work (Lee et al. 2009) on the
use of engineered viruses as templates to make, at room temperature, high-rate
FePO4 /single-walled carbon nanotube electrodes. Biological principles will be,
in the years to come, more intensely implemented in the rational design and
assembly of battery components, and this is a good thing that we must pursue.
All the abovementioned systems are Li based, and we cannot remain insensitive
to the controversial debates about Li resources and more so regarding low-cost
ones. Today’s lithium comes from brines, mainly located in Chile and Bolivia

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3235

(Meridian International Research 2006, 2008). Foreseen feedstock considerations

already blow the whistle on Li resources, with the risk that they could not cope
over the next decades with the increasing Li demands dictated by automotive
transportation and grid-related applications. Alternatively, Li can be found in
unlimited quantities in sea water; but, its recovery is more tricky and expensive
than extracting it from brines via a concentrating step that just requires solar
energy, as is done today. In anticipation of such a scenario, new chemistries must
be envisioned, and the most appealing alternative relies on the use of Na instead
of Li, as such an alkali metal is resource unlimited and easy to recuperate.
Sodium has already been successfully implemented in today’s commercialized
high-temperature Na/S cells for MW storage or Na/NiCl2 ZEBRA-type systems
for EVs, both of which take advantage of highly conducting Na-b-alumina
ceramics. Mindful of these considerations, the development of a room-temperature
Na-ion cell should be feasible. At present, we do not see any obstacles to
achieving Na-ion cells, as long as part of our research community is willing to
deviate from the appealing Li-ion technology, and search for both positive and
negative Na-insertion electrodes. Highly oxidizing positive Na-electrode materials
(Na0.44 Mn2 O4 ; Na2 FePO4 F) (Ellis et al. 2007) capable of acting as a sodium
reservoir do exist; in contrast, designing materials capable of inserting Na at
a low potential remains to be an untouched field. It is then left to the solid-state
chemist’s intuition, coupled with the theorist’s guidance to break new ground in
this new research. It should therefore be put forward that Na-ion cells, which
could use either liquid, ionic or solid electrolytes, will always fall short of meeting
energy densities of the Li-ion counterparts, as Na is heavier than Li and is less
reducing (e.g. lower potential). For large-volume applications, such drawbacks are
overcompensated by the low cost of Na associated with its unlimited resources.

(d) Means to achieve sustainable and greener Li-ion batteries

Besides the aforementioned considerations of materials abundance and
syntheses, which inflict a lower carbon footprint, the concept of renewable
electrodes is becoming increasingly important and more so as battery recycling
will become mandatory owing to the foreseeable mass production dictated by the
EV market. The recycling of batteries from regular solid wastes is a thermal-
recovery process that, in addition to raw-material extraction and electrode
processing, adds further energy consumption to the battery life-cycling cost. To
eschew such difficulties, an idealistic foreseeable view for battery processing in
the years to come could consist (figure 4) of using electro-active organic electrode
materials synthesized from ‘green chemistry’ concepts through low-cost processes
free of toxic solvents; this will also enlist the use of natural organic sources
(CO2 harvesting entities) as precursors, which will be biodegradable and easily
destroyed by combustion (providing CO2 ), so that the battery assembly/recovery
process will have a minimum CO2 footprint (Chen et al. 2008).
Going deeper into the notion of sustainability and renewable electrodes,
our group recently explored the field of organics in the hope of unravelling
organic molecules that show attractive electrochemical characteristics in terms
of voltage and energy density. With respect to positive electrodes, we revisited
the old chemistry of oxocarbons with special attention to the lithium rhodizonate
(Li2 C6 O6 ) phase (Chen et al. 2008). Such a molecule, within which carbon

Phil. Trans. R. Soc. A (2010)

3236 J.-M. Tarascon

CO2
ba
rec ttery
+
ycl
ing

biomass
_
tery
bat bly
em
ass
extraction
elaboration via
green chemistry

Figure 4. Schematic for battery assembling and recycling with zero carbon footprint. It enlists
the use of natural precursors, which are easy to extract and which could be transformed into an
electrochemical active electrode material via ‘green chemistry’. Later, upon recycling, the battery
will liberate the CO2 that will be used for further biomass production (courtesy of P. Poizot).

atoms are bonded to carbonyl oxygen atoms, was found to present performances
with a capacity of 540 mAh g−1 greatly exceeding the one of today’s LiCoO2
positive electrode (150 mAh g−1 ). Besides, such an electrode has the advantage
of being fully sustainable since it is made from the oxidation of a carbohydrate,
named myoinositol, which can be made from natural products, more specifically
from the disphosphorylation of phytic acid. At this juncture, let us recall that
phytic acid is widely distributed in plants and accounts, for instance, for 8 per
cent of the dry weight of corn-steeping liquor. Further screening for electro-
active organic molecules versus Li+ /Li0 showed molecules having carboxylate
groups conjugated with the molecule core (Armand et al. 2009), such as lithium
terephtalate (Li2 C8 H4 O4 ); the latter shows a capacity (340 mAh g−1 ) approaching
that of the carbon negative electrode (372 mAh g−1 ) presently used in Li-ion cells,
while having safety advantages and an irreproachable environmental benefit, since
it could be made by recycling the ubiquitous plastic polyethylene terephtalate.
An Li-ion cell, based on fully renewable positive and negative organic
electrodes, showing an acceptable level of performance, was recently assembled
(Chen et al. 2009).
However, as usual with any new concept, they have their pitfalls, and this
one is no exception. Besides the solubility issue associated with the use of single
molecules rather than monomers or polymers, there is the need to isolate a multi-
functional organic molecule whose Li salt could be oxidized while being air stable.
Indeed, although Li2 C6 O6 contains two Li+ ions, they cannot be electrochemically
removed since, upon oxidation, the compound falls apart liberating, among
others, CO2 and forming carbonates. What is wanted are Li-bearing molecules
capable of undergoing a reversible insertion–de-insertion reaction at a potential

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3237

X2
y
lit
abi
in
sta
su

Li–air
energy density

250 Wh kg–1, 800 Wh l–1

cathodes (nano)

Li–S
conversion
A123

cathodes
organics

chemistry
Sony

Na-ion
Sony
Sony

1990 1995 2005 2007 2015 2020 future future future

??

Figure 5. The battery technology landscape as personally believed. For obvious reasons, the time
scale is left open since bringing a new concept to commercial fruition bears some uncertainties.
Even with an aggressive projection, whatever the type of technologies considered, we solely propose
a two-fold increase in energy density over the next 30 years, and this will most likely come from
the Li–air system. For applications from which cost and materials resources are crucial, organic Li
ion and Na ion will play an important role in the years to come. It should therefore be stated that
such predictions do not take into account complete out-of-the box solutions to electrochemically
store electricity, but some of the concepts related to the latter are hopefully maturing in a few
laboratories.

exceeding 3.2 V. Organic electrodes have been criticized in the past for their poor
performances, the reason why they fell into oblivion. Therefore, owing to their
renewable aspects, combined with their performances amenable to those of the
present Li-ion electrodes, we view them as the most wanted electrodes in years
to come to make Li-ion batteries with no carbon footprint.

(e) Means of increasing capacity while ensuring sustainability and green storage
The renewable aspect brought out by organic electrodes nicely secures Li-
ion technology in terms of sustainability and greenness. Performance-wise
(gravimetric energy density, life cycle and power rate), such electrodes can
easily be amenable to the performance of today’s best inorganic electrodes,
but chances of outpacing them in terms of energy density are very slim. In
the long term, improving the Li-ion technology while preserving its sustainable
aspect will require out-of-the-box solutions. Metal–air systems (Zn–air, Al–
air and more so Li–air) have long been recognized as great candidates for
achieving staggering energy-density increases. However, despite the efforts that
went into these technologies, very little progress has been made regarding their
reversibility so that they rapidly fell into oblivion. Using the most attractive Li–
air system as a reversible battery must at least clear three scientific/technological

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3238 J.-M. Tarascon

hurdles: (i) designing efficient oxygen electrodes knowing that confectioning such
electrodes has been a nightmare for fuel cells, (ii) ensuring the development of
electrode formulations that are capable of solvating oxygen and are stable with
respect to the superoxide anions, and (iii) mastering the Li–electrolyte interface
that we could not solve for the last 25 years within the field of Li batteries, the
reason why the presently successful Li-ion battery technology has surfaced in the
first place. Solving all of these at once is a colossal task that will require several
years of cooperative research. However, tremendous progress in developing Li-
ion technology can be witnessed, and convincing data showing the possibility of
achieving reversibility does exist (Debart et al. 2008). The oxygen electrode in an
Li–air cell mainly consists of a carbon mat-supported catalyst, which serves as
the host structure for the reversible formation of Li2 O2 according to the following
reaction: 2Li+ + 2e− + O2 → Li2 O2 . Mindful of the various approaches developed
with the field of Li-ion batteries to design nanocomposites/nanoarchitectured
electrodes, together with rapid screening of new catalysts having special shape,
structures and morphology, P. Bruce’s group (Debart et al. 2008) has succeeded
in preparing electrodes that display for a few cycles (figure 4) reversible capacities
as high as 1000 mAh g−1 , this corresponds to a six- to eight-fold increase when
compared with today’s LiCoO2 electrodes. However, prior to implementing Li–
air-powered cars, a number of engineering and chemical challenges, such as
improving the lifecycle of this electrode, together with its energy efficiency
(e.g. reducing the 1 V upset between subsequent charges/discharges cycles),
together with designing appropriate electrolytes and mastering the Li interface,
have to be overcome. Optimism must therefore prevail owing to the increasing
number of groups becoming involved with the Li–air system following Bruce’s
pioneering work.
Another attractive system in terms of performances and sustainability, which
has been around for more than two decades, is the Li–S system. Similar
to the Li–air system, sulphur instead of oxygen is reduced at the positive
electrode (S + 2Li+ + 2e− → Li2 S) to produce solid Li2 S instead of solid Li2 O2 ,
with the difference that sulphur is solid and not gaseous like oxygen. Present
Li–S cells show a better cycle life and greater efficiency (0.2–0.4 V between
subsequent charge and discharge) than the Li–air ones, although their intrinsic
energy density is lower. Their main drawback relies on the formation of soluble
polysulphide (LiSnx) species during reduction leading, upon subsequent cycling,
to a progressive detrimental capacity fade. To eschew such a difficulty, carbon
mesoporous nanoarchitectured electrodes, loaded with sulphur via an injection
process, were successfully designed, showing better cycle life than any previously
reported S electrodes (Ji et al. 2009). Overall, Li–air and Li–S technologies share
the same problems, and this is beneficial, as any advance in Li–air can be directly
implemented in Li–S and vice versa. Their penetration into the market is a few
years ahead, with LiS most likely being the first one.

2. Conclusions

Batteries have been around for more than 200 years, and they are increasingly
becoming part of our everyday life. Nevertheless, they are constantly criticized for
their poor performances as they can never meet users’ unconditional demands.

Phil. Trans. R. Soc. A (2010)

 Review. Future Li-ion research trends 3239

Thus, progress in battery research is frequently in the spotlight, as energy storage

is far from following Moore’s law (doubling of the storage capacity in 18 months)
that dictates memory storage. In spite of all this, we hope to have conveyed,
through this article, the message that the landscape of battery energy research
is rapidly changing worldwide. Researchers are leaving traditions behind and
searching for new concepts embracing fundamental studies. The implementation
of electrodes, enlisting raw abundant elements made via eco-efficient processes or
obeying the renewable concept with zero carbon footprint, together with recent
advances in sustainable and green Li–air systems, is shaping a bright future for
electrochemical storage over the years to come. Although risky, we dared share,
as personally perceived, our view of the battery landscape for the next decades
(figure 5). Regardless of the fact that future predictions are very hard, it is a
certainty that sustainable and greener Li-based storage technologies will no longer
be science fiction in the years to come. Achieving such a next generation of storage
technologies will eagerly require interdisciplinary approaches, and our success will
depend on how good we are in setting cross-fertilization between these different
disciplines.
Addressing energy-related issues is a worldwide problem shared by many
countries. Nevertheless, while targeting similar objectives and having similar
road maps, various countries have tendencies to favour national over worldwide
programmes. Time is limited, and it is urgent for our politics to find
means/infrastructures to enhance the cross sharing of information between
national programmes dealing with energy-related matters, both at the European
and international levels. Concrete actions must be rapidly taken if we want to
secure a bright future for the generations to come and to our planet as a whole.
The author greatly thanks both the LRCS and the ALISTORE-ERI members for enthusiastic and
fruitful discussions that have enabled the identification of both challenges and possible research
directions listed in this paper.

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