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E
lectrochemical energy storage systems,
which can deliver electricity on
demand, lie at the heart of todays
mobile electronic devices and electrically
powered vehicles. On a larger scale,
such systems can secure the supply of
renewable energy through the bufering of
intermittent resources such as wind and the
Sun. Te growing need for energy storage
systems has prompted intense academic
research activities and huge industrial
investments in the feld of rechargeable
batteries
1,2
. Te lithium-ion battery, which
was introduced by Sony Corporation in
1991, now plays a major role in consumers
SOLID ELECTROLYTES
Lithium ions on the fast track
The solvent-based electrolytes used at present in lithium-ion batteries can be unsafe for large-scale applications.
A crystalline electrolyte with high ionic conductivity could soon enable all-solid energy storage systems.
Christian Masquelier
M
A
T
E
R
I
A
L

W
I
T
N
E
S
S
When fullerene chemistry took of
in the 1990s, one enticing use of
the carbon-cage molecules was as
a protective wrapping for trapped
molecules, isolating them from their
environment. Tis, it was suggested,
might ofer a kind of matrix-isolation
technique for studying sensitive
chemical species under ambient
conditions a notion explored
previously using other cage complexes
1
.
Trapped metal atoms the frst class
of endohedral fullerene compounds
reported might be used as contrast
agents for magnetic resonance imaging,
or perhaps even as qubits for quantum
computing
2,3
. If encapsulation could be
made reversible, maybe fullerenes could
be used to chaperone drug molecules to
their target cells.
Some of these possibilities continue
to show promise; no doubt others will
turn out to have been over-optimistic.
Te enterprise of trapping molecules
to study in isolation has now been
furthered signifcantly by Kurotobi
and Murata, who have used inventive
chemistry to open up a hole in C
60
,
insert a single water molecule, and
then seal up the cage again
4
. Tey
report a crystal structure of H
2
O@C
60

(the @ sign denoting encapsulation)
complexed to a nickel porphyrin,
with the lone H
2
O localized in the
cage centre.
Kurotobi and Murata suggest that
H
2
O@C
60
might ofer a rare opportunity
to study the water molecule in a
situation where it is not coordinated to
other species via either hydrogen bonds
or lone-pair dative bonding. Well,
perhaps. Te nominally hydrophobic
interior of the fullerene cage might
certainly lead one to imagine that the
water molecule behaves almost as if
invacuo. And the ultraviolet-visible
spectrum of the complex is almost
identical to that of empty C
60
, suggesting
almost no interaction between the
H
2
O and the carbon cage, while the
13
C
NMR spectrum shows all the carbons
to be identical, indicating that the water
molecule rotates rapidly on the NMR
timescale. Yet it would be surprising
if indeed there was no interaction
between the hydrogen atoms and the
aromatic rings of the cage, as hydrogen
bonding to the electrons of benzene
rings has been reported for other
encapsulated water molecules, both in
synthetic supramolecular complexes
5

and in a hydrophobic protein cavity
6
.
Its in the latter regard that H
2
O@
C
60
might prove to be a useful model
compound. Several proteins have
hydrophobic interior spaces in which a
few water molecules might lodge. In the
cytokine interleukin-1, for example,
such a cavity hosts between oneand
four water molecules on average
6
. Tere
is predominantly a water dimer in the
cavity itself, but it is not totally isolated:
lone water molecules in two channels
opening onto the cavity sometimes
connect the dimer to the exterior
7
.
Such trapped water molecules seem
to have signifcantly slowed dynamics
relative to the bulk
8
, although its
not clear whether this depends on
there being several water molecules
present so that the dynamics become
cooperative. If thats so, the trapped
water might be expected to have a
diferent dielectric constant from the
bulk, altering its solvent properties
9
. If
the same chemistry will work for larger
fullerenes, Kurotobi and Murata might
have devised a valuable method for
exploring the characteristics of such
small, hydrophobically encapsulated
water clusters.
References
1. Cram, D.J., Tanner, M.E. & Tomas, R.
Angew. Chem. Int. Ed. 30, 10241027 (1991).
2. Harneit, W. Phys. Rev. A 65, 032322 (2002).
3. Ju, C., Suter, D. & Du, J. Phys. Rev. A 75, 012318 (2007).
4. Kurotobi, K. & Murata, Y. Science 333, 613616 (2011).
5. Atwood, J.L., Hamada, F., Robinson, K.D., Orr, G.W. &
Vincent, R.L. Nature 349, 683684 (1991).
6. Somani, S., Chng, C.P. & Verma, C.S. Proteins
67, 868885 (2007).
7. Yu, B., Blaber, M., Gronenborn, A.M., Clore, G.M.
& Caspar, D.L. D. Proc. Natl Acad. Sci. USA
96, 103108 (1999).
8. Modig, K., Rademacher, M., Lcke, C. & Halle, B.
J.Mol. Biol. 332, 965977 (2003).
9. Despa, F., Fernndez, A. & Berry, R.S. Phys. Rev. Lett.
93, 228104 (2004).
CAGED WATER
PHILIP BALL
2011 Macmillan Publishers Limited. All rights reserved
650 NATURE MATERIALS | VOL 10 | SEPTEMBER 2011 | www.nature.com/naturematerials
news & views
everyday life, and it is regarded as the key
technology for the further development
of hybrid or all-electric cars
2,3
. It followed
the demonstration of facile and reversible
lithium-ion insertion and extraction
from LiCoO
2
(the positive electrode)
and graphite (the negative electrode),
respectively. Besides the positive and
negative electrodes, the electrolyte through
which the ions move during charge and
discharge cycles has a critical role in the
performance of lithium-ion batteries. It is
the subject of extensive scrutiny, because it
impacts the safety, toxicity and long-term
cyclability of such high-energy-density
electrochemical storage systems
4
. Writing
in NatureMaterials, Kamayaetal.
5
now
report the discovery of a crystallized solid
inorganic electrolyte whose lithium-ion
conductivity even exceeds that of solvent-
based systems, and which can be applied in
all-inorganic energy storage systems.
Te high operating voltage of a
lithium-ion electrochemical cell (~4V)
prohibits the use of aqueous electrolytes,
and most commercial cells use solutions
of dissociated salts such as LiPF
6
, LiBF
4

or LiBC
4
O
8
in organic alkyl carbonate
solvents. Tese solvents are usually
complex mixtures of ethylene-, dimethyl-,
diethyl- and ethylmethyl carbonates with
additives. Despite the great advances in
volumetric and gravimetric energy and
power density that have been made, such
electrolyte compositions pose a number
of challenges, in particular for large-
scale applications in electric vehicles or
stationary energy storage. At high operating
voltages, these electrolytes can undergo
unwanted reactions with electrodes
made from structurally unstable layered
transition-metal oxides that are detrimental
to the long-term cyclability of such energy
storage systems. Furthermore, they may
decompose and generate dangerous thermal
runaways
4
. Many alternatives to purely
organic solvent-based liquid electrolytes
have hence been proposed in the literature,
and some have been implemented in real
batteries. Tese materials include solid
polymers, ionic liquids, inorganic (ceramic)
electrolytes and their combinations in
so-called hybrid electrolyte systems,
which, however, still sufer from slow ionic
transport (particularly at low temperature)
and high cost
6
.
Te new inorganic crystallized
composition that Kamayaetal. report
Li
10
GeP
2
S
12
shows the highest lithium-
ion conductivity ever measured for a solid,
about 12mScm
1
at 300K. Te material
possesses a three-dimensional structure
that consists of (Ge
0.5
P
0.5
)S
4
tetrahedra,
PS
4
tetrahedra, LiS
4
tetrahedra, and LiS
6

octahedra. Based on careful structural
determination from powder neutron
difraction data, the researchers at Tokyo
Institute of Technology and Toyota Motor
Corporation found highly anisotropic
conduction of Li
+
ions along one crystal
direction, namely through partially
occupied LiS
4
tetrahedra and interstitial
positions that are connected by a common
edge (see Fig.1). Tey derive a low
activation energy for ionic conduction
(24kJmol
1
) in this new material, which
enables its use at low temperature and
leads to a conductivity of 10
3
SCm
1
at
245K. Moreover, a wide electrochemical
stability versus Li
0
is demonstrated, which is
particularly important for cycling stability
and safety issues, which have been major
drawbacks in existing systems such as
Li
3
N, Li
1/3x
Li
3x
NbO
3
, LiTi
1.7
Al
0.3
(PO
4
)
3

and LiBH
4
LiI superionic conductors.
Finally, the researchers realize all-solid-
state batteries using LiCoO
2
and indium
as positive and negative electrodes,
respectively, which operate at 3.3V with
excellent reversibility.
Te results by Kamayaetal.
demonstrate how continuous investment
into energy storage systems such
as the 30-year-long efort that
Japanese authorities and companies in
particular have made in lithium-ion
technology can lead to signifcant
breakthroughs arising from previously
disregarded chemistries. Other examples,
which were inspired by the pioneering
work of Takahashi
7
, include sulphide
glassy and crystallized compositions in
the Li
2
SSiS
2
LiI, Li
2
SSiS
2
Li
3
PO
4
and
Li
2
SGeS
2
P
2
S
5
systems
8,9
.
Most certainly, the work of
Kamayaetal. will be followed by further
studies from other groups, as the
implementation of the new superionic
conductor Li
10
GeP
2
S
12
in real lithium-ion
energy storage systems will be contingent
on, for instance, the large-scale ceramic
processing of air-sensitive sulphides, the
cost-efective use of Ge and the mechanical
stability of such a battery over prolonged
cycling. Overall, the work of Kamayaetal.
will probably stir signifcant and renewed
interest in ceramic solid electrolytes,
and it may lead to breakthroughs similar
to the discoveries of beta alumina and
NASICON-type structures, which
are nowadays used in NaS batteries.
Recent demonstrations of all-solid-state
batteries
9,10
illustrate the wide variety
of chemistries and ceramic processing
techniques that could be envisaged to
further improve the performance of
energy storage systems based on this
new solid electrolyte, for example by
reducing the interfacial resistance between
active components.
Christian Masquelier is at the Universit de Picardie
Jules Verne, Amiens, France.
e-mail: christian.masquelier@u-picardie.fr
References
1. Yang, Z. etal. Chem. Rev. 111, 35773613 (2011).
2. Tarascon, J.M. & Armand, M. Nature 414, 359367 (2001).
3. Armand, M. & Tarascon, J.M. Nature 451, 652657 (2008).
4. Hammami, A., Raymond, N. & Armand, M. Nature
424, 635636 (2003).
5. Kamaya, etal. Nature Mater. 10, 682686 (2011).
6. Knauth, P. Solid State Ionics 180, 911916 (2009).
7. Takahashi, T. & Yamamoto, O. Electrochim. Acta
11, 779789 (1966).
8. Kanno, R. & Murayama, M.J.Electrochem. Soc.
148, A742A746 (2001).
9. Tatsumisago, M. & Hayashi, A. Funct. Mater. Lett. 1, 3136 (2008).
10. Aboulaich, A. etal. Adv. Energ. Mater. 1, 179183 (2011).
+ -
In
e

>
LiCoO
2
Li
10
GeP
2
S
12
Li
+
Li
+
Li
+
Li
+
Li
+
Li
+
Li
+
Li
+
Figure 1 | Schematic view of the all-solid-state lithium-ion battery reported by Kamaya and colleagues.
During charging, lithium ions (grey) travel with high mobility from the positive LiCoO
2
electrode to the
negative indium electrode via partially occupied LiS
4
tetrahedra and interstitial positions in the new
superionic conductor Li
10
GeP
2
S
12
(ref.5).
2011 Macmillan Publishers Limited. All rights reserved