Ionogels, Ionic Liquid Based Hybrid Materials

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This journal is c The Royal Society of Chemistry 2011 Chem. Soc. Rev., 2011, 40, 907925 907
Cite this: Chem. Soc. Rev., 2011, 40, 907925
Ionogels, ionic liquid based hybrid materialsw
Jean Le Bideau,
a
Lydie Viau
b
and Andre Vioux*
b
Received 30th July 2010
DOI: 10.1039/c0cs00059k
The current interest in ionic liquids (ILs) is motivated by some unique properties, such as
negligible vapour pressure, thermal stability and non-ammability, combined with high ionic
conductivity and wide electrochemical stability window. However, for material applications, there
is a challenging need for immobilizing ILs in solid devices, while keeping their specic properties.
In this critical review, ionogels are presented as a new class of hybrid materials, in which the
properties of the IL are hybridized with those of another component, which may be organic
(low molecular weight gelator, (bio)polymer), inorganic (e.g. carbon nanotubes, silica etc.) or
hybrid organicinorganic (e.g. polymer and inorganic llers). Actually, ILs act as structuring
media during the formation of inorganic ionogels, their intrinsic organization and
physicochemical properties inuencing the building of the solid host network. Conversely, some
eects of connement can modify some properties of the guest IL, even though liquid-like
dynamics and ion mobility are preserved. Ionogels, which keep the main properties of ILs except
outow, while allowing easy shaping, considerably enlarge the array of applications of ILs. Thus,
they form a promising family of solid electrolyte membranes, which gives access to all-solid
devices, a topical industrial challenge in domains such as lithium batteries, fuel cells and dye-
sensitized solar cells. Replacing conventional media, organic solvents in lithium batteries or water
in proton-exchange-membrane fuel cells (PEMFC), by low-vapour-pressure and non ammable
ILs presents major advantages such as improved safety and a higher operating temperature range.
Implementation of ILs in separation techniques, where they benet from huge advantages as well,
relies again on the development of supported IL membranes such as ionogels. Moreover,
functionalization of ionogels can be achieved both by incorporation of organic functions in the
solid matrix, and by encapsulation of molecular species (from metal complexes to enzymes) in the
immobilized IL phase, which opens new routes for designing advanced materials, especially
(bio)catalytic membranes, sensors and drug release systems (194 references).
1. Introduction
Ionic liquids (ILs) are organic salts which exhibit low melting
temperature, by convention below 100 1C. They consist of
only ions; their properties are strikingly dierent from those of
molecular liquids. One of the most important properties is
negligible vapour pressure (and generally thermal stability and
non-ammability). Actually, the physicochemical properties
of ILs can be tuned by the choice of the anion-cation pair,
which opens millions of possibilities.
1,2
ILs have been widely
used by electrochemists for a long time, as a result of their high
ionic conductivity (within 10
4
to 8.10
2
S cm
1
around room
temperature) and their wide electrochemical potential window
(which can be as high as 5.7 V between Pt electrodes).
3,4
A
renewed interest for such electrolytes, which prove to be
high-performance over a wide range of temperatures (typically
up to 200300 1C), has been triggered by the topical demand in
advanced electrochemical devices, such as actuators, lithium
batteries, electric double-layer capacitors, dye-sensitized solar
cells and fuel cells.
5
Moreover, the unique combination of non-volatility and
favourable solubilising characteristics of ILs has motivated a
growing interest as a replacement for organic solvents, and more
generally of volatile organic compounds (VOCs), in many
industrial applications like catalysis
6,7
and extraction.
8
Actually,
negligible vapour pressure allows easy retrieval of the nal
products by distillation or by using biphasic chemical processes,
without degradation or loss of solvent by evaporation and,
consequently, an easy recycling. Thus, the use of ILs appears
sustainable and they have been claimed (maybe too loosely) as
a
Institut des Materiaux Jean Rouxel (IMN),
Universite de Nantes - CNRS, 2 rue de la Houssinie`re, BP 32229,
F44322 Nantes, France. E-mail: Jean.LeBideau@cnrs-imn.fr;
Tel: +33 240 373 919
b
Institut Charles Gerhardt de Montpellier,
UMR 5253 CNRS-UM2-ENSCM-UM1, Universite Montpellier 2,
Place Euge`ne Bataillon Montpellier, cc1701, F34095, France.
E-mail: Andre.Vioux@univ-montp2.fr; Tel: 33 4 67 14 39 70
w Part of the themed issue on hybrid materials.
Chem Soc Rev
Dynamic Article Links
www.rsc.org/csr CRITICAL REVIEW
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908 Chem. Soc. Rev., 2011, 40, 907925 This journal is c The Royal Society of Chemistry 2011
green solvents. To what extent ILs are actually environment
friendly is in debate nowadays. Nevertheless benign ILs have
been recently synthesized from biomolecules.
9,10
Anyway,
considerable developments have been carried out in organic
chemistry, especially in the eld of homogeneous catalysis by
organometallic complexes and biocatalysis, as in many cases
ILs bring about some improvement of catalyst eciency and
selectivity.
1113
On the other hand, although ILs easily dissolve inorganic
species as well, their use as solvents in inorganic chemistry is
much more recent. Actually, they have proved to be an
innovative reaction media, especially in metal electro-
deposition,
14
ionothermal syntheses (ILs enable reaction
temperatures above 300 1C without autoclaving)
15,16
and
solgel.
17
There have been numerous studies on the controlled
growth of nanoparticles in ILs, especially metal nanoparticles
in relation to their catalytic activity in organic reactions.
18
The
use of ILs in the preparation of a wide range of inorganic (and
hybrid) materials (including silicas, organosilicas, metal
oxides, metal chalcogenides, metal salts, open-framework
structures, nanostructured metals and alloys etc.) has been
recently reviewed.
1921
The growing use of ILs in the materials eld originates from
their unique structural and physicochemical features. The
local organisation of ILs (or ILs containing solutes) involves
uxional ion aggregates that are stabilized by ionic inter-
actions as well as hydrogen bonds and van der Waals forces.
22
A short overview on physicochemical properties of ILs, which
sets the background of all applications based on ILs, is given
in the rst part of the article in the form of a tentative
outline of the current understanding of structure-properties
relationships.
There is currently a challenging need for immobilizing ILs in
solid devices, while keeping their unique properties. To this
purpose, one possibility is to impregnate a support, the IL
being used as an adsorbed lm. This approach, which is
beyond the scope of this article, is well illustrated by the
current development of supported IL catalysis (SILC), in
which metal catalysts are immobilized within IL lms
supported on silica beads, resulting in free owing powders
that are particularly suitable for continuous xed-bed reactors.
SILC has been widely reviewed.
23,24
Another way of
immobilization involves the formation of a three-dimensional
network which percolates throughout the IL and is responsible
for the solid-like behaviour of the resulting material, called
ionogel (or ion gel). Actually, if any gel may be regarded as
solid and liquid phases percolating throughout each other,
here the specicity is the negligible vapour pressure and the
thermal stability of the liquid phase, which makes ionogels
stable materials over time and allows for using them up to
temperatures much higher than ambient.
Jean Le Bideau (born 1965)
obtained his Materials Science
Degree from the Universite de
Nantes (France), and then
joined the Institut des
Materiaux de Nantes under
the supervision of Professor
Jean Rouxel, where he
received his PhD in 1994. After
two years stay at Michigan
State University (USA) under
the supervision of Professor
Daniel G. Nocera, he moved
to the Universite de Montpellier
(France) as Associate
Professor, and returned in 2008 to the Universite de Nantes as
full Professor. His research is aimed at building low dimensional
organicinorganic materials with specic connement eects.
Since 2003, he focuses his research on solgel chemistry in ionic
liquids, more specically on the properties of the resulting
conned ionic liquids.
Jean Le Bideau
Lydie Viau earned a degree in
chemical engineering in 2000
from the Ecole Nationale
Superieure de Procedes et
dIngenierie Chimiques dAix-
Marseille (France) and a PhD
degree in organometallic
chemistry in 2003 under the
supervision of Dr Hubert Le
Bozec at the University of
Rennes. She spent one year at
the University of Canberra
(Australia) and one year at
the University of Nantes
(France) before joining the
group of Professor Andre Vioux at the Institut Charles Gerhardt
in Montpellier (France). Her current research interest mainly
focus on the development of ionogels based on silica and
polymers suitable for catalysis, drug delivery, electrolyte
membranes.
Lydie Viau
Andre Vioux studied chemistry
at the University of Montpellier
and completed his PhD in
coordination chemistry in 1981
under the supervision of Prof.
Robert Corriu. In 198384 he
worked at the University of
Paris 6 on solgel chemistry
under the supervision of Prof.
Jacques Livage. In the late
80s, he developed some new
approaches to out-of-equilibrium
ceramics by thermal conversion
of silicon-containing polymer
resins at the University of
Montpellier, where he has been full Professor since 1992. Over the
last decades he has focused his research on new ways to inorganic
organic hybrid materials and on solgel processing in unusual media.
Andre Vioux
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The various types of ionogels may be separated into
physical and chemical gels. In physical gels, the internal 3-D
network is cross-linked through weak (reversible) interactions
(e.g. hydrogen bonds, hydrophobic interactions, crystallite
junctions etc.), whereas in chemical gels the cross-linkage
results from covalent bonding. Physical gels can be obtained
by using an organic gelator (molecular species of low
molecular mass or polymers as well) or a divided solid (e.g.
fumed silica particles, carbon nanotubes) which coagulate the
whole assembly. As a matter of fact, free-standing membranes
can be prepared by incorporating an IL into a polymer.
25
However, physical gels are often in the form of jellies, slurries
or pastes, or at the least, present a limited mechanical solidity.
Another possibility is to create chemical gels, by conning the
IL in a covalently interconnected network. Typically, the
chemical cross-linking of the above mentioned polymers
results in mechanically resistant organic matrices. Alternatively,
chemical gels based on inorganic oxide matrices may be
prepared by solgel synthesis from an alkoxide precursor.
Interestingly, the structural and textural properties of the
inorganic matrix may be strongly inuenced by the presence
of the IL.
17
A third way, which has just emerged, involves
nanocomposite matrices in which the polymer or biopolymer
network is cross-linked via covalently bonded oxide nanollers
generated in situ by solgel.
26,27
The dierent ways of obtaining
organic, inorganic or nanocomposite ionogels are reviewed in
the second part of the article.
It is worth underlining that the intrinsic hybrid character of
ionogels relies on the intimate combination of an IL and a
solid-like network. The properties of ionogels are expected to
derive both from those of the IL and those of the component
forming the solid-like network. As mentioned above, this
component may be organic (polyethylene oxide, cellulose
etc.), inorganic (carbon nanotubes, silica etc.) or organic
inorganic (silsesquioxane etc.). However, properties may be
aected by the nanometre scale assembly. This is the case in
some ionogels based on organic polymers, in which only one
glass transition is observed at a temperature (Tg) lower than
that of the pure polymer and higher than that of the pure IL.
28
This behaviour is typical of plasticizing eects.
29
The eects of
connement that are observed in inorganic ionogels are much
more specic. Actually, physicochemical properties of the
IL, as phase transitions and molecular dynamics, may be
signicantly modied by the connement in the nanopores
of the host matrix. These specic connement eects are
presented in the third part of the article.
Ionogels, which keep the main properties of ILs except
outow, considerably enlarge their array of applications.
Some of these applications, which range from solid electrolytes
to drug release to catalysis (Fig. 1), are reviewed in the fourth
part of the article. They are generally based on the intrinsic
properties of ILs, such as ionic conductivity, drug activity and
solvent ability. These properties can be adjusted to specic
tasks by the choice of the anion-cation combination. Blending
adds a further possibility of tuning. Moreover, the encapsulation
of designed molecules (catalysts, sensing molecules, uorescent
metal complexes etc.) in the immobilized IL phase opens
innite possibilities of functionalization. The host matrix
and its interactions with IL ions bring their own contribution
to the whole functionality. Finally, polymer tractability as well
as versatility of solgel in shaping allows easy adaptations to a
wide range of devices.
2. Relationships between structure and
physicalchemical properties of ILs
ILs can be dened as aprotic or protic, depending on the
nature of cation. The former class arises from quaternization
reactions. Typically aprotic ILs involve organic cations as
imidazoliums, pyridiniums and phosphoniums (Fig. 2). Protic
ILs arise from a proton transfer to the same site occupied by
an alkyl group in aprotic ILs. Note that this transfer between a
Brnsted acid (AH) and a Brnsted base (usually an amine) is
equilibrated, which implies the presence of some residual
neutral species.
30
However, the displacement of equilibrium
towards ion formation may be maximised using 2 : 1 or 3 : 1
acidbase ratios. Indeed the oligomeric anionic species
(A
2
H
or A
3
H
2
) that formed are weaker bases than the

monomeric anion (A
), because of solvation by the additional

acid molecules.
31,32
The uidities, and attendant conductivities,
of protic ILs tend to be much higher than those of aprotic
ILs.
33
Within a given family of ILs, the physicochemical
properties can be tuned by the choice of the anion
(e.g. hydrophilicity, Fig. 2). Typically halide anions can be
Fig. 1 Ionogels, multi-purpose hybrid materials.
Fig. 2 Some examples of cations and anions used in the formation of
aprotic ILs and changes of water miscibility with anion type.
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exchanged by metathesis reaction or converted into complex
anions by Lewis acid addition (Fig. 3).
34
However, even if the preparation of ILs involves quite
simple organic chemistry, their purication is far from being
straightforward, since both distillation and crystallization can
not be easily used. Then, small amounts of impurities
have been shown to dramatically inuence their properties.
Accordingly, since the development of purication methods
of water-stable and air-stable ILs is relatively recent,
reliable data on their physicochemical properties are still
incomplete, despite a huge number of reports. A comprehensive
overview of physicochemical properties of ILs is far beyond
the scope of this article. The only purpose here is to give the
non-specialist reader a glance at the current approaches
to rationalize the fundamental physicochemical properties
of ILs.
Among the interactions taking place in ILs, Coulombic
interactions are predominant, insuring their high cohesive
energy and, therefore, their extremely low vapour pressure.
There are evidences of ionic association in ILs and,
consequently, all ions could not be available to contribute to
conductivity. Typically, ion pairs, if suciently long lived,
appear neutral in the electric eld. A fundamental point relies
in the balance between anion-cation interaction and their
respective volume.
35,36
The empirical Waldens rule connects conductivity per mole
of charge carrier L = sV
e
(where s is the specic conductivity
in S cm
1
and V
e
is the volume per equivalent) to the uidity
(i.e. the reciprocal viscosity Z
1
) of the electrolyte medium,
stating that LZ = C, where C is a temperature dependent
constant. A way of evaluating the concept of ionicity in ILs
(i.e. the eective fraction of ions available to contribute to
ionic conduction) would be to compare the Walden plot of ILs
(i.e. the logarithmic plot of L vs. Z
1
) to that of a so-called
ideal electrolyte solution (where the ions are assumed to be
fully dissociated), typically a 0.01 M aqueous KCl solution.
However, one has to keep in mind that the Waldens rule
applies to innitely diluted electrolyte solutions. Nevertheless,
quite unexpectedly, the Walden plot of ILs, which are the very
opposite extreme from diluted electrolyte solutions, discloses
excellent correlation between viscosity and conductivity.
35
Deviations from the Walden rule (Fig. 4),
37
have been
discussed in term of ionicity (from good to poor ILs
and non-ILs),
35
as a decrease in ionicity of ILs should bring
about an increasing deviation from the so-called ideal KCl line
(slope 1 through the origin).
Actually, the Walden plot represents a qualitative approach.
Other authors proposed a more quantitative approach by
dening the self-dissociativity of ILs as the molar conductivity
ratio (L
imp
/L
NMR
), calculated from the molar conductivity
measured by the electrochemical impedance method
(L
imp
, L in the Walden plot approach) and that estimated by
use of pulse-eld-gradient spin echo (PGSE) NMR, ionic
self-diusion coecients L
NMR
.
38
The molar conductivity
(L
NMR
) can also be calculated from the ionic self-diusion
coecients (D
+
and D
), using the NernstEinstein equation,

which for a 1 : 1 salt can be written as:
L
NMR

N
A
e
2
kT
D
1
where N
A
is the Avogadro number, e is the electron charge on
each ion carrier, k is the Boltzmann constant, and T is the
absolute temperature. This statement is based on the assumption
that every diusing species detected by PGSE-NMR contributes
to the molar conductivity. On the other hand, L
imp
is related
to the migration of charged species in an electric eld. Thus,
the L
imp
/L
NMR
ratio would reect the ionicity. Note
that the diusion coecients of each ion are given by the
StokesEinstein equation:
D
kT
6pZr
2
where r is the eective ionic radius. Interestingly, if one
substitutes these diusion coecients into the above Nernst
Einstein equation, one obtains a relationship in the form:
L constant Z
1
1
r
1
r

3
Actually, this relationship provides a renement of the Walden
plot which takes into account the radius (i.e. the volume) of
the conductive species. Ionicity was estimated from the
vertical distance of the data points to the reference KCl line
for a range of aprotic ILs. A relative good agreement with
L
imp
/L
NMR
was obtained.
39
Finally, a measurement of the ionicity of ILs would be
provided by the eective ionic concentration (C
e
), which is
the product of L
imp
/L
NMR
and the molar concentration. For
1-alkyl-3-methylimidazolium ILs [C
n
MIm][TFSI], C
e
was
found to decrease from 3.1 to 1.5 10
3
mol cm
3
as the
number of carbon atoms n in the alkyl chain increases from
1 to 8. This decrease in ionicity cannot be explained in terms
of Coulombic interactions, but it can be understood considering
the interactions between the alkyl chains. Actually, small to
wide angle X-ray scattering (SWAXS) evidenced the
occurrence of nanoscale structural heterogeneities whose sizes
depend on the length of the alkyl chain and are related to
chain segregation into nano-domains.
40
Interestingly, computer
simulations predicted structuring in a manner that is analogous
to microphase separation between polar and nonpolar
domains.
41
Thus, the short-range structuring of ILs arises
from a balance of long-range (Coulombic) and short-range
(hydrogen bonding, van der Waals, dipoledipole, pp)
interactions. As a consequence, ILs may be regarded as
solvents, but also as supramolecular networks in which the
introduction of other species takes place with the formation of
Fig. 3 Typical preparations of imidazolium ILs by metathesis
reaction and Lewis acid addition.
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inclusion-type compounds between the guest molecules and
the host pre-organised medium (ILs).
22
Note that the presence
of H-bonded nanostructured networks, with polar and
non-polar regions, may be responsible for the stabilisation of
enzymes supported in ILs, which can maintain their
functionality under very extreme denaturative conditions.
13
Discussing the concept of ionicity is beyond the scope of this
review. However, it is worth underlining here that Abbott
proposed a model in which charge transport is governed by the
mobility of holes at innite dilution, which explains why the
Walden rule has been found to be applicable to ILs, and why
the application of the StokesEinstein equation allows accurate
prediction of their conductivity.
42
Actually, the ions are not
closely packed, allowing some cavity volumes to exist, although
at a very low (about 10
6
) molar fraction. At a given
temperature, these holes are of random size and location and
undergo constant ux. An ion will be able to move only if there is
a hole of suitable dimensions adjacent to it. The assumption is
that this occurrence is rate-limiting for the ionic conduction.
3. Preparation of ionogels
Synthetic routes to ionogels fall into three categories depending
on the nature of the solid-like network, which may be organic
(using low molecular weight gelators or polymers), inorganic
(typically using oxide nanoparticles, carbon nanotubes or
oxide networks arising from solgel), or hybrid organic
inorganic (typically polymers reinforced with inorganic llers)
(Fig. 5).
3.1 Organic ionogels
3.1.1 Use of low molecular weight gelators. Low molecular
weight gelators (LMWGs) are organic molecules, which are
added in small quantities to liquids at elevated temperature
and then induce physical gelation upon cooling. Actually
LMWGs are able to self-assemble in solution through
supramolecular bonding such as hydrogen bonding, pp inter-
actions or electrostatic interactions.
Fig. 4 (a) Walden plot of log(molar conductivity, L) against log(reciprocal viscosity, Z
1
), which includes the classication for ILs proposed by
Angell et al.
35
and (b) a close-up view of the region occupied by typical aprotic ILs. The solid line indicates the ideal line for a completely
dissociated strong electrolyte aqueous solution (KCl
aq.
). Reprinted with permission from ref. 37.
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Thus, Kimizuka et al. studied the gelation of ether-containing
ILs by the addition of L-glutamic acids or carbohydrates such
as b-D-glucose, a-cyclodextrin.
43
Formation of brous nano-
structures was observed due to strong interactions between
carbohydrates and ether groups. Shinkai used a cholesterol
based compound known to aggregate by one-dimensional
stacking of the cholesterol moieties.
44
However, this molecule
turned out to be poorly soluble in ILs; accordingly acetone
co-solvent was needed. Yanagida and co-workers reported
ionogels arising from an imidazolium IL and N-benzyloxy-
carbonyl-l-isoleucyl aminooctadecane as a gelator. They
applied these electrolyte gels to the fabrication of a dye-
sensitized solar cell (DSSC) which showed light-to-electricity
conversion eciency of 5% and high temperature durability.
45
Hanabusa et al. synthesized clyclo(dipeptides) gelators from
aspartame which allowed gel formation of a wide variety of
ILs, including imidazolium, pyridinium, pyrazolidinium,
piperidinium, morpholinium and ammonium salts, by using
less than 1 wt% of gelator.
46
Recently the rst organo-
metallic gelator, a pyridine-bridged bis(benzimidazolylidene)-
palladium complex, proved ecient in the gelation of a variety
of ILs.
47
Gelation was shown to involve p-stacking, van der
Waals interactions and metal-metal bonding. Dong et al. used
bis(4-acylaminophenyl)methane and bis(4-acylaminophenyl)-
ether with varied acyl chains to gelify imidazolium ILs.
48
The
phase transition temperatures of the gels increased with an
increase of the acyl chain length of the gelators, whereas the
conductivities of ionic-liquid gels decreased. However, the
dierences in conductivities between the gels and corresponding
bulk ILs were within one order of magnitude.
3.1.2 Polymer gels. The use of polymers to immobilize ILs
in the form of free-standing membranes which combine the
mechanical exibility of a polymer and the characteristic
conductivity of ILs has been widely developed, particularly
as materials for electrochemical devices. Many gelled systems
are obtained simply by swelling a polymer in an IL
49
or mixing
the polymer and the IL together with a co-solvent which is
subsequently removed. Another route is the polymerization of
monomers in an IL used as a solvent, but the loss of miscibility
above a certain degree of polymerization may be a
limitation.
50
Of course, the key point is the miscibility between the IL and
the polymer.
29
However, numerous ILs have been reported to
act as plasticizers, by lowering the glass transition temperature
(T
g
) which thus provides exibility. Thus, the outstanding
compatibility of imidazolium salts with poly(methyl
methacrylate)s (PMMA) has been reported.
28,50,51
Fig. 6
illustrates the improvement in thermal stability of PMMA
ionogels compared with that of PMMA itself, despite
of a decrease in the T
g
with the incorporation of
IL ([C
4
MIm][TFSI]). However, poly(ethylene oxide)s (PEO)
and uoropolymers and copolymers, as sulfonated tetra-
uoroethylenes (Naon
s
) and poly(vinylidene uoride-co-
hexauoropropylene)s (PVdF-HFP), have attracted the most
interest as host polymers in electrolyte membranes for lithium
batteries, fuel cells and dye-sensitized solar cells.
52,53
Even in
the case of complete miscibility,
29
there is a limitation
associated with the plasticizing eect which entails the loss
of mechanical resistance on increasing the IL loading.
Cross-linking permits the improvement of mechanical stability
without losing signicant conductivity.
5456
The limitation related to non miscibility is well illustrated by
the connement of ILs in epoxy-based networked polymers
performed by curing epoxy resins with an amine in the
presence of an IL.
57
The materials obtained exhibited
threshold behaviour at 40 wt% loading of IL, moving from
insulating with a high Youngs modulus to ion conducting
with a low Youngs modulus, which reected the transition
from discrete microdroplets to a percolating phase of IL in the
polymer network. Accordingly, the IL was easily extracted
with acetone by means of Soxhlet extractor at high IL loading
(4 40 wt%), whereas it was retained at lower IL loading.
The obstacle of non miscibility is hard to bypass (e.g. by
using the polymerization of IL-based microemulsions),
58
as
the long-term operation of the membranes remain subjected to
the risk of some leakage of IL. On the other hand, in some
cases cross-linked resins with permanent macroporosity could
be prepared by using the IL as a porogen solvent.
59
Another
interesting way to take advantage from non miscibility is the
use of some polymer-IL binary systems that exhibit phase
separations depending on external stimuli (as temperature) to
access to smart ionogels. Thus, poly(benzylmethacrylate)
(PBzMA) and its copolymers exhibit lower critical solution
temperature (LCST)-type phase separation in common hydro-
phobic ILs.
60
Moreover, cross-linked PBzMA gels show
reversible and discontinuous volume phase transition in
[C
2
MIm][TFSI] with the change in temperature. Lodge et al.
reported the self assembly of tri-block copolymers that
alternated soluble and insoluble polymer blocks and yielded
transparent thermoreversible ionogels (Fig. 7).
61,62
The recent
application of ionogels derived from tri-block copolymers as
gate dielectric in polymer thin-lm transistors evidences high
potential in exible electronics.
63
The key point is that
ionogels are both printable and have tremendous specic
capacitances, in excess of 10 mF cm
2
, which is 500 times as
high as many typical dielectrics and 10 times as high as some
other recently reported dielectric layers.
Special mention has to be made of the use of biopolymers,
as gelatin and polysaccharides, which provides sustainable
materials, furnished with biomolecular functions.
43,64,65
It is
worth stressing here that the dissolution of high molecular
weight polysaccharides, especially cellulose, is a challenge of
great importance in sustainable chemistry context.
66
ILs do
Fig. 5 Dierent types of ionogels.
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oer a route to such an aim, thanks to the ability of some
anions, as chloride at high concentration, to break the original
intra- and inter-chain hydrogen bonding of polysaccharides.
67
Typically, cellulose completely dissolves in water-soluble
1-butyl-3-methylimidazolium chloride on microwave pulse
heating (120170 1C).
68
Solvation involves hydrogen bonding
between the carbohydrate hydroxyl protons and the
chloride ions in a 1 : 1 stoichiometry, as demonstrated by
Fig. 6 (a) TG curves for MMA network polymers with dierent mole fractions of dissolved [C
2
MIm][TFSI] and [C
2
MIm][TFSI] bulk at a heating
rate of 10 1C min
1
. From ref. 50. (b) DSC thermograms for MMA network polymers with dierent mole fractions of dissolved [C
2
MIm][TFSI]
and [C
2
MIm][TFSI] bulk at a heating rate of 10 1C min
1
. Reprinted with permission from ref. 50.
Fig. 7 An ABA triblock copolymer with soluble B block (blue) and insoluble A blocks (red) (left) self-assembles in the presence of an IL
(+ and symbols) to form an ion gel (center). Suitable choice of A block enables thermoreversible gelation when the A blocks become soluble at a
higher temperature (right). Reprinted with permission from ref. 62.
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13
C and
35/37
Cl NMR relaxation measurements.
69
Cellulose
can be regenerated in water.
68
Otherwise, gelation simply
occurs by keeping the IL solution at room temperature for a
few days under ambient humidity.
70
Gels are similarly
obtained from chitosan,
71
agarose,
72
and starch
73,74
or by
mixing a solution of cellulose with starch or carrageenans.
75,76
3.2 Inorganic ionogels
3.2.1 Bucky gels. Carbon nanotubes (bucky tubes)
consist of a rolled-up graphene sheet with heganonally
arranged sp
2
-hybridized carbon atoms and provide good
electronic and optical properties. CNTs possess extraordinary
mechanical, electrical and thermal properties, however one
major drawback is that they are hard to process. One
approach to increase the solubility and processability is to
absorb organic molecules onto their surfaces.
In 2003, Aida and Fukushima found that single walled carbon
nanotubes (SWNTs) could be easily dispersed in imidazolium
ILs, where heavily entangled bundles of carbon nanotubes were
exfoliated to give highly dispersed, much ner bundles.
77
Gelatinous materials were obtained by grounding the IL and
SWNTs, followed by centrifugation to remove the excess of IL.
Phase transition and rheological properties suggested that the
gels are formed by physical cross-linking of the nanotube
bundles, mediated by local ordering of the ILs rather than by
entanglement of the nanotubes. The bucky gels thus obtained
are easy to process into any shape. Another method included the
heating and ultrasonication of CNTs in the presence of the IL at
90 1C.
78
The dispersion mechanism for SWNTs in ILs is still
unclear. A possible cationp interaction between the surface of
SWNTs and the imidazolium IL was postulated. However,
recent experiments and simulation studies inferred that the IL
interact with SWNTs through weak van der Waals interactions,
cationp or electrostatic interactions.
79
Anyway, bucky gels
opened a wide range of applications, as they combine electro-
conductive CNTs and ion conductive ILs.
80
3.2.2 Silica-based ionogels. Silica-based ionogels can be
obtained either by dispersion of silica nanoparticles into ILs
or by solgel processing.
Dispersion of silica nanoparticles. Numerous studies
reported a striking stabilization of metal nanoparticles in
ILs, even in the absence of any stabilizers, such as surfactants
or polymers.
20
Nevertheless, bare silica colloids were shown to
be unstable in ILs, leading to the formation of a close packed
particulate network. This gelation of ILs in the presence of
silica nanoparticles was rst used by Graetzel to prepare
thermally stable quasi-solid electrolytes.
81
Later on, Honma
studied the ionic conductivities of gels obtained using 10 wt%
of [C
4
MIm][TFSI] and evidenced the importance of particles
size on gelation.
82
Studies on the mechanism responsible for
the colloidal aggregation demonstrated a reaction-limited
cluster aggregation, suggesting a moderate repulsive-
interaction between the particles, which was not enough to
stabilize the particles due to extremely high ionic strength and
the resulting surface-charge screening.
83
Solgel processing. The rst solgel synthesis in an IL
solvent was reported in 2000 by S. Dai et al., which prepared
mesoporous silicas with high surface areas from a
mixture of tetramethoxysilane (TMOS) and formic acid in
[C
4
MIm][TFSI].
84
Actually, the IL, which was removed at the
end of the synthesis, was used as a template. Since this
pioneering work, numerous solgel syntheses involving IL
templates were reported.
17,85,86
ILs proved to have signicant
inuence on the structure of the resulting silica-based materials.
The eect of ILs as drying control chemical additives was
ascribed to the formation of a non volatile liquid lm on the
walls of pores which could protect them from the interface
strains associated with the formation of a meniscus on
evaporation.
87
This would permit the pore walls to strengthen
on ageing, before removing the IL by means of Soxhlet
extraction or calcination thus giving access to highly porous
structure.
Anyway, this approach is out of the scope of this review.
Solgel processes involving silicon alkoxide precursors, in
which the interstitial IL phase rst present between colloidal
particles is then entrapped as condensation cross-linking
extends, should result in more intimate biphasic systems than
the simple impregnation of oxide particles. In this view, Deng
and co-workers reported the immobilization of a catalyst IL in
silica gels prepared in the presence of HCl aqueous
solutions,
88,89
while some of us developed high ionic conducting
solid membranes by adapting the non-aqueous solgel method
of Dai.
9092
The latter way provided monolith ionogels, cast as
pellets or rods, which turned out to be endowed both with the
transparency and mechanical properties of silica, and the
conductivity performances of ILs (about 3 10
2
S cm
1
at
200 1C).
91
Recently, monolithic silica ionogels endowed with
both ionic conductivity and electronic conductivity: were
obtained by incorporating multiwalled carbon nanotubes
(MWNT).
93
It is worth noting that the MWNT percolation
was reached with a rather low loading (i.e. 3.6 wt%), and
exhibited an electronic conductivity of 1.31 10
2
S cm
1
at
room temperature.
Alternatively, the IL could be extracted from ionogels by
polar solvents such as acetonitrile, then exchanged for a new
IL phase.
94
Care was taken to keep the solvent of extraction
inside the material to avoid cracking and nally the solvent
was replaced by the new IL. This method makes it possible to
incorporate any (even sensitive to formic acid) metal complex
within the ionogel, opening the route to many applications as
sensors and display devices. Thus, an ionogel showing a very
intense and highly monochromatic red photoluminescence
under UV irradiation, was obtained by doping an europium(III)
tetrakis b-diketonate complex into an imidazolium IL and by
immobilizing the IL in a silica-like network.
95,96
Derived from the above working up, ionogels could also be
obtained by synthesizing the silica gel in a classical molecular
solvent, then exchanging this solvent for an IL. Recently, this
method was successfully applied by Taubert using a basic
catalyzed solgel reaction.
97,98
Dynamics and physical
properties of the IL nanophase conned in silica-like matrices
will be developed in next section.
Inorganic matrices other than silica. Quasi-solid systems
arising from the mechanical mixing of inorganic particles as
titania or caesium hydrogen sulfate and ILs have been used as
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electrolyte materials.
99,100
Parallel to silicon alkoxides, solgel
reactions of metal alkoxides in ILs were also investigated.
They turned out to be an interesting route to oxide particles,
with control of morphology and crystalline form.
101
Thus,
Dionysiou systematically studied the synthesis of highly
porous titanium oxide particles with anatase crystalline structure
from a titanium isoproxide precursor by hydrolytic solgel
reaction at room temperature in the presence of water
immiscible 1-butyl-3-methylimidazolium tetrauorophosphate
[C
4
MIm][PF
6
].
102
However, anatase monoliths with a
worm-like pore structure and large surface areas were
prepared using [C
4
MIm][BF
4
] as a templating agent by a
classical solgel method associated with a peptization process
in the presence of an aqueous solution of HCl.
103
Actually, the
only report relevant to ionogels was the recent preparation of
TiO
2
gels froma mixed emulsion of 1-butyl-3-methyl-imidazolium
bis(triuoromethylsulfonyl)imide [C
4
MIm][TFSI], TiCl
4
,
methanol and formic acid, which was ultra-sonicated at
25 1C, then aged and dried at 80 1C.
104
These electrolyte
materials showed stable ion conductivities over a wide range of
temperatures, including the intermediate region of 100200 1C,
and thermal stability at 275 1C (conductivity of 10
2
S cm
1
at
275 1C). Tin dioxide translucent monolith ionogels were
obtained by using a b-diketonato stabilized tin precursor.
105
A major advantage of this precursor over commercially
available SnCl
4
was the possibility to use a wide range of
ILs ([C
4
MIm][BF
4
], [C
4
MIm][PF
6
], [C
4
MIm][Br]), thanks to
the chelating ligand on the tin precursor which permitted to
control the polycondensation rate.
3.3 Composite (hybrid organicinorganic) ionogels
To our knowledge, the association of molecular organogelators
and inorganic nanoparticles has been hardly explored.
However it is worth mentioning the latent chemically-cross-
linked gel electrolyte precursors for quasi-solid dye sensitized
solar cells (DSSC) reported by Kato et al.
106
The gel electro-
lyte precursors consisted of silica or titania nanoparticles and a
dicarboxylic acid (typically with a C
16
chain) as the latent
gelators. The viscosity of the precursor was low at rst,
but when the precursor was baked at 80 1C, it solidied
immediately.
By contrast, the incorporation of inorganic nanoparticles in
polymer ionogels is widely used, as it is well known to improve
the mechanical properties. Accordingly, it is a way of counter-
balancing the plasticizing eect of high IL loadings, while
preserving exibility and tractability of the resulting
nanocomposite materials. It is worth mentioning here the
use of imidazolium ILs as compatibilizers between apolar
polymer chains and polar inorganic ller, as clays
107
and
silica
108
(see also the specic case of carbon nanotubes
109
).
Although this use does not enter the scope of the review, it
sheds light on the role that may be played by ILs in some
ternary polymer/inorganic ller/IL systems. Moreover,
nanocomposite polymer electrolytes (NCPEs) have demonstrated
enhanced ion conducting properties.
110114
Actually, inorganic
oxide nanollers have large specic surface areas covered with
various Lewis acidic or basic groups. The interactions between
these surface groups and the ionic species are most likely
involved in the observed conductivity enhancement. Typically
the creation of a large IL/oxide interface is thought to promote
ion-pair dissociations (for instance by giving rise to specic
interactions with the anion or the cation) and to provide some
free volume for ions to diuse. Moreover, mesoporous silica
llers lead to higher lithium transference numbers in electro-
lyte membranes for Li-ion batteries.
114
Recently, an in situ
solgel synthesis of silica nanollers has been successfully used
to prepare transparent and exible electrolyte membranes.
27
Indeed, the use of modied poly(methyl methacrylate)s
(PMMA) bearing pendant trimethoxysilane groups and tetra-
ethoxysilane (TEOS) allowed immobilizing high loadings of
IL, while silica nanollers covalently bonded to the polymer
chains provided mechanical strength. Note that the inorganic
functionalisation of cellulose with siloxane groups, which can
subsequently undergo polycondensation, was shown to
similarly yield ionogels with hybrid organicinorganic host
matrices.
26
4. Connement eects
The connement of ILs, where ion-wall interactions become
important relatively to ionion interactions, can infer some
changes in their physicochemical behaviour. The rst insight
into the eect of connement is given by the thermal
behaviour. Typical phase transitions disclosed on bulk ILs
by DSC analysis (on heating after a fast cooling) comprise
glass-transition temperature (T
g
) (the compound passed
from the glass state to a subcooled liquid phase), cold
crystallization (T
cc
; exothermic), and melting (T
m
; endothermic).
In silica ionogels, while glass transition is observed whatever
the degree of connement, no hint of any cold crystallization
nor melting is observed for the highest degrees of connement
(i.e. the smallest space for the IL).
91,92
Moreover, rst-order
transitions are clearly shifted. In ionogels, melting (T
m@pore
)
is shifted to lower temperatures, although the signal
simultaneously broadens.
115
Such a displacement of phase
transition has been reported for many conned solvents, but
the lowest shift observed with ILs is greater than the highest
observed with molecular liquids (conversely with the viscosity
behavioursee below).
116
This shift is commonly related to
the melting temperature of the conned species (T
m
), the pore
diameter (d), the molar volume (V
m
), the enthalpy of fusion
DH
f
, the surface tensions at solid-substrate g
ss
and liquid-
substrate g
ls
interfaces on the basis of the GibbsThomson
equation T
m
T
m@pore
= a(T
m
V
m
/DH
f
)(g
ss
g
ls
)/d.
91,115
The
dependence on the chemical nature of the host matrix is thus
expected. Actually, it appears that there is a strong dependence
of thermal behaviour on the chemical nature of both pore
walls and IL ions.
98
Note that CNTs oered an opportunity to
observe unique crystalline organisation due to specically
strong CH F contact with the uorinated anion in the
crystal phase induced by the strong connement degree.
78,117
It is also noteworthy that related simulation studies of
connement of [C
1
MIm][Cl] conned between hydrophobic
graphene sheets showed a transition at much higher temperatures
than expected for the bulk IL, moreover at a distance of the
wall of no less than 1.1 nm.
118
This evidences the particularly
important eect of the liquid-substrate anity on transition
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temperature in the case of ILs (attractive forces increase the
melting point of conned species; conversely, repulsive forces
decrease it), concurrently with the degree of connement
(volume of conned species vs. volume of connement) which
decreases the melting point.
119
Moreover, it is noteworthy that
recent rheology studies on conned ILs between mica walls
(SFA apparatus) showed strong IL-surface interaction below
around 10 nm, i.e. below around 13 IL organized layers
(depending on the nature of the IL, gures are given here
for [C
4
MIm][TFSI]).
120
As referred to the above mentioned
DSC studies, this appears to be a limit below which connement
shows strong eects. Other recent rheological studies conclude
at a lower viscosity enhancement for connement of ILs as
compared to that of connement of non-polar molecular
liquids,
116
or more precisely to a strong lowering of the
viscosity for [BMIm] based ILs conned between methylated
mica walls compared to non-methylated parent walls.
121
Solid state NMR spectroscopy gives further information on
the molecular dynamics of conned ILs. From a general point
of view, when increasing the temperature, the IL system
transforms from the rigid lattice to more dynamic phenomena
associated with the diusive state: this change is accompanied
by a line narrowing of the NMR signals, which normally takes
place at the melting point in case of crystalline salts and at the
glass transition temperature in case of amorphous materials.
So, as a rst approach, following the line width gives insights
into the dynamics of IL. Whatever in polymer gels or silica
conned ILs, connement usually results in decreasing the
temperature at which the line narrowing occurs (
1
H and
19
F
nuclei).
91,122
This shows that the connement studied did not
inhibit ion dynamics.
1
H NMR spectra of conned IL showed a relatively narrow
signal without spinning on monolithic silica ionogels
(Fig. 8a).
123
Unusual for solids, this evidenced that liquid-like
mobility was still enough to average the dipoledipole and
chemical shift anisotropy (csa) which were responsible for line
broadening. A spinning rate as low as 400 Hz was enough to
recover liquid-like resolution, although the signal was not as
narrow as for bulk IL due to susceptibility gradient at the
wall neighbourhood. Other studies on similar systems (weak
interactions between conned IL and pore wall) pointed out
an even better resolution, concluding to the absence of a
noticeable wall eect.
97
From the spectra observed without
spinning and at a spinning rate of 400 Hz, it was concluded
that the dynamics of the conned ionic liquid experienced only
a slight slowing down. It is noteworthy that the above
mentioned MAS NMR experiments probe short-range
correlations, which is consistent with the distribution of
chemical shifts at the wall neighbourhood. Relaxation-time
measurements were used to probe longer spatial range correlations
(Fig. 8b).
1
H T1 relaxation times measured above the melting
temperature showed similar T1 for conned and bulk IL, thus
illustrating similar dynamics. Nevertheless, below the
temperature of crystallisation of bulk IL, T1 parameter of
conned IL exhibited values in the same range as above the
crystallisation temperature, thus revealing that liquid-like
behaviour was gained toward lower temperatures on connement.
Further proton and uorine nuclear magnetic relaxation
dispersion (NMRD) studies, widening space and time
scales probed to 20 nm and 5 ms, respectively, suggested a
translational diusion of this conned cation and anion at the
proximity of the at pore surface. From a model, translational
time (time during which an ion is correlated with the surface)
and escape time (time during which the ion is not correlated to
the surface) were measured and showed a decrease of the
translational correlated time along with an increase of the
ratio escape time/translational time when increasing the
temperature.
124
PFG NMR studies showed also that conning
an IL or conning an IL-based electrolyte (i.e. with addition of
lithium salt) does not entail the ionic mobility.
125
The ionic conductivity of silica ionogels with rigid porosity
is of course of interest. While complex impedance spectro-
scopy (CIS) allows ionic conductivity measurements, ions
transportations throughout the ionogel has been demonstrated
with lithium battery prototypes as well as with solar cells.
126
By means of CIS, the ionogels showed conductivity of the
same order of magnitude as that of bulk IL. Typically, the
conductivity of a monolithic ionogel was found to be roughly
half that of the conned IL, for the same shape factor, which
means very similar conductivities. The Arrhenius plots
recorded between ca. 30 1C and +220 1C showed break
slopes as reported by several studies.
9092,125
The origin of this
Fig. 8 (a)
1
H NMR room-temperature spectra of the pristine IL ([C
4
MIm][TFSI]) and a monolithic silica ionogel (IL/SiO
2
= 0.5) at zero, 400 Hz
and 3kHz spinning rates (asterisks indicate spinning sidebands). (b)
1
H relaxation times vs. temperature of pristine IL (open symbols) and of a
monolithic silica ionogel (IL/SiO
2
= 0.5; black squares). Reprinted with permission from ref. 123.
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break slope is not completely elucidated and could be related
either to ion pairs dissociation or to the disappearance of
wall-to-ions interactions, as seen by NMRD.
124
Infra-red spectroscopy on silica based ionogels indicated no
striking dierence between the bulk and conned ILs.
97
Nevertheless, in the case of imidazolium ILs with long alkyl
chains, the shifts of the bands assigned to ~ n(CH
2
) disclosed
some changes in the conformational order of the alkyl chain,
which were ascribed to a more disordered conformation
adopted on connement compared with the bulk crystalline
solid IL at room temperature.
94
Similarly, Raman spectra
disclosed that, after being conned in mesoporous silica,
[C
4
MIm][Cl] was in the liquid form as early as 25 1C, whereas
it was expected to melt at 70 1C.
94
These results, which are
consistent with DSC and NMR data, conrm that steric
constraints at the wall neighbourhood prevent solid state
organization of the IL at low temperature.
83
Nevertheless, it
has to be emphasized that the conclusions from the spectro-
scopic studies presented just above refer to connement at no
less than B6 nm but that a uorescence red shift was observed
recently in one study for smaller pore diameters, i.e. higher
connement.
127
Luminescence spectroscopy was informative too. An
unexpected connement eect was observed specically with
a dicyanamide-based IL. Fluorescence emissions were
recorded with dierent IL loadings; the emission intensity of
a 25 wt% [C
4
MIm][N(CN)
2
] ionogel was found to be about
200 times stronger than that of bulk [C
4
MIm][N(CN)
2
]. This
was tentatively attributed to the presence of strong pp
conjugations.
94
It could be inferred that a specic arrangement
of the ions at the wall neighbourhood led to a specic
anionanion arrangement, which in turn led to this unexpected
uorescence enhancement. Another indirect way to probe the
physical feature of a conned species was to compare the
luminescence spectrum of an europium(III) complex dissolved
in an IL conned in a silica matrix with that of the same
europium(III) complex dissolved in the bulk IL. No dierence
in crystal-eld ne structure or in relative intensities could be
observed in the spectra of the ionogel and the IL solution. This
indicated that connement of the europium(III)-doped IL had
negligible inuence on the structure of the europium(III)
complex. The decay time turned out to be similar in the bulk
(0.55 ms) and conned IL (0.52 ms).
95
The luminescence decay
times of others lanthanide(III) cations (samarium, neodymium,
ytterbium, erbium, terbium) encapsulated in ionogels were
similarly recorded. No signicant dierence between the decay
times (conned IL or bulk) was observed, evidencing again the
liquid-like behaviour of the conned IL.
128
5. Applications
5.1 Electrolytic membranes
ILs are of considerable interest to implement advanced
electrochemical devices, specically energy devices, whose
development is expected to address the topical challenges
of renewable energy and global warming, as lithium
batteries, fuel cells and solar cells. Actually, replacing
conventional media, organic solvents in batteries or water in
proton-exchange-membrane fuel cells (PEMFC), by low-
vapour-pressure and non ammable ILs presents major
advantages such as, among others, improved safety and
operating temperatures higher than 100 1C. Immobilizing
ILs within solid membranes gives access to all-solid devices,
which are an industrial challenge for practical applications.
Lithium-ion batteries. Lithium batteries are expected to nd
a prominent role as electrochemical storage systems in
renewable energy plants, as well as power systems for sustainable
vehicles, such as hybrid and electric vehicles. However, scaling
up the lithium battery technology for these applications is still
problematic since issues such as costs, wide operational
temperature and safety are still to be resolved. The latter point
attracts a special attention since a too rapid discharge of a
lithium battery or a short-circuit can result in overheating,
rupture, and even explosion. The current development of
all-solid IL-based lithium batteries may be regarded as a real
breakthrough in the eld (Fig. 9).
129
Actually, IL-polymer systems, commonly referred to as gels
in the literature, showed performances in term of number of
cycling, rate of cycling and solid electrochemical interface
formation which were similar to those obtained with non
conned IL-based electrolytes.
130
The connement of a mixed
salt (IL with lithium salt) within a poly(vinylidene uoride)
hexauoro propylene (PVdFHFP) copolymer matrix has
been intensively studied.
131
It is here of importance to obtain
exible, thin (lowering the ohmic drop), mechanically resistant
(avoiding short-cuts upon pressure between the positive and
the negative electrode) membranes. It was shown that the
conductivity in these polymeric matrices, e.g. PVdFHFP
membranes loaded with an electrolyte solution of LiTFSI
in N-butyl-N-ethylpiperidinium N,N-bis(triuoromethane)-
sulfonimide [PP24][TFSI], was on the order of 10
4
S cm
1
at room temperature, which resembled that of the parent
bulk electrolyte under the same conditions. However, an
Fig. 9 Toward all-solid IL based lithium battery. Reprinted with
permission from ref. 129.
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unexpected but potentially signicant enhancement in Li
transference number was observed in passing from the liquid
to the membrane electrolyte system. Another polymer
which was intensively studied for hosting lithium salt or ILs
containing lithium salt is polyethylene oxide (PEO), in relation
to its ability to solvate Li cation. The addition of IL to
P(EO)
20
-LiTFSI systems resulted in an increase of more than
one order of magnitude in ionic conductivity at room
temperature (moving from salt-in-polymer to polymer-in-
salt systems).
132
In this case, with a N-butyl-N-methyl-
pyrrolidinium [PY14] to lithium cations ratio of 3.2, the
ionic conductivity of the polymer electrolyte reaches
2 10
4
S cm
1
at 40 1C. Moreover, a low temperature
conductivity enhancement of the ILs containing-PEO
electrolytes was pointed out, which was attributed to the
formation of amorphous phases instead of PEO-lithium
crystalline phases.
Another approach is the solgel hydrolysis-polycondensation
of silicon alkoxide directly onto a porous electrode. This
allows a full wetting of the porosity of the composite electrode
as well as the simultaneous formation of a solid electrolytic
separator.
126
The concept allows single-step preparation of the
assembly of the electrode and solid electrolyte separator and
can be applied without specic adaptation to current thick
electrode technology prepared by the widespread tape casting
technique. Here the polarization, i.e. the voltage dierence
between charge and discharge, was less important with the
ionogel electrolyte than with genuine IL-based electrolyte,
which was attributed to the good wetting of the composite
electrode by the ionogel. Moreover for LiNi
1/3
Mn
1/3
Co
1/3
O
2
based electrodes, the discharge capacities obtained were
B110 mAh g
1
and B105 mAh g
1
with the ionogel
and IL based electrolytes resp., whereas with classical
carbonated based electrolytes the capacities were found
around 125 mAh g
1
. Nevertheless, up to now the main
drawback remains the low cycling rate (C/20 at RT). It is also
interesting to note that the capacity of a battery with LiV
3
O
8
as positive electrode and with PEO-PVdF conned IL-based
electrolytes exhibited a (slight) increase, as referred to those
observed for this cathode material in standard electrolytes.
133
This result was attributed to a lower solubility of the electrode
material in the IL-polymer electrolyte.
Fuel cells. Protic ILs can serve as proton carriers in fuel cell
electrolytes (Fig. 10), thus giving access to conductivities
exceeding 10 mS cm
1
under fully anhydrous conditions.
134,135
For instance, ammonium salts can be used as protic
electrolytes for fuel cells running above 80 1C.
136
Actually,
conventional PEMFCs require medium temperature operation
in order to provide more ecient power generation and longer
lifetime.
137
Moreover, PEMFCs also require membranes
eciently separating both fuels. In this prospect, providing
membranes with proton conducting ionic liquids (PCILs), non
volatile and non degradable in the needed range of temperature,
is the focus of intense research.
138
Most recent research has been devoted to PVdF-HFP,
Naon
s
and sulfonated polyimide ionogel-membranes. The
latter ones have been recently studied with diethylmethyl-
ammonium triuoromethanesulfonate for FC operating under
nonhumidied conditions at intermediate temperatures. Using
an IL weight loading as high as 80%, these membranes
showed thermal stability (4300 1C), ionic conductivity
(410
2
S cm
1
at 120 1C), mechanical strength and gas
permeation comparable to those of hydrated Naon
s
.
139
Naon
s
membranes were probably the most studied for FC
applications. In these membranes the choice of the IL and the
version of Naon
s
are important. The sensitivity of the choice
of the PCIL is exemplied by the comparison of two ILs with
the same diethylmethylammonium cation associated with
either triuoromethanesulfonate or TFSI anion: the rst one
showed good activity for FC electrodes reaction as well as
relatively low ohmic drop, leading to open circuit voltage
(OCV) of 1.03 V at 150 1C, whereas the second showed lower
electrode activities, leading to an open circuit voltage of ca.
0.7 V.
140
Modied Naon
s
were also shown to be of
interest. Thus connement of triuoromethanesulfonate
triethylammonium in Naon
s
neutralized with triethyl-
ammonium resulted in lower water uptake and improved
thermal and mechanical stability as compared to the reference
Naon
s
membrane.
141
The key role of ionomer-IL inter-
actions on the proton transference number has been recently
emphasized.
135,142
Polymer membranes based on PVdF-HFP
were also developed. A marked decrease in conductivity,
larger than what could be expected from the dilution of the
conducting IL by the insulating polymer matrix, was ascribed
Fig. 10 IL based polymer electrolytes fuel cells. Reprinted with permission from ref. 140.
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to the morphology of the membrane and the interactions
between the polymer matrix and the IL.
143
Superacids
like triuoromethanesulfonic acid or N,N-bis(triuoro-
methanesulfonyl)imide were used to enhance proton
conductivity. Unfortunately, strong interaction between
HTFSI and parent IL (with the same anion) increased the
viscosity and accordingly decreased the ionic conductivity.
144
Also based on a uorinated polymer, uorohydrogenate ionic
liquid based membranes showed OCV around 1.0 V at 130 1C
with interesting conductivity at 34.7 mS cm
1
at 130 1C.
145
Hybrid inorganicorganic nanocomposites were also
investigated. Biopolymer composites were fabricated, aiming
at increasing proton transport by blending a basic chitosan
exchange membrane and basic oxide llers such as CaO.
146
Filling Naon
s
with SiO
2
particles led to an unexpected
segregation into Naon
s
domains with helical chains and
hydrophilic domains where SiO
2
particles were shown to be
covered by a shell of PCIL.
147
Finally, a recent work was reported on electrolyte
membranes fully based on silica-derived ionogels.
148
Tetraethoxysilane/ethyl-triethoxysilane/trimethylphosphate and
1-butyl-3-methylimidazolium-bis(triuoromethylsulfonyl)imide
were used as precursors. The sol was then cast onto one
side of the Pt-loaded carbon serving as electrode. The
resulting membrane showed good hydrogen permeability
(2.7 10
12
mol cm
1
s
1
Pa
1
for the 40 wt% [C
4
MIm][TFSI]
at 150 1C). Nevertheless, the main drawback of such a
membrane still resides in the occurrence of cracks which would
short-cut the gas path.
Solar cells. Still in the sustainable development context,
harvesting solar energy with a high yield is a major challenge
because of the clean, inexhaustible and ready availability of
the resource.
149
In the ionogel prospect, physical gels obtained
by mixing silica nanoparticles as gelator to solidify IL-based
electrolytes (with addition of KI and I
2
) resulted in enhanced
performances of dye sensitized solar cells (DSSCs) (Fig. 11).
As a matter of fact, such ionogels were applied to DSCCs
based on a ruthenium polypyridyl photosensitizer leading
to 7% eciency at AM 1.5 sunlight.
81
Ionogels provide
considerable benets over bulk ILs since they enable the
fabrication of exible, all solid-state devices, free of leakage
and available in varied geometries. At the borderline of
ionogel, it is worth mentioning DSSCs in which the IL-based
electrolyte wetted an array of TiO
2
nanotubes perpendicular to
a Ti foil, thus enhancing electron transfer. The photovoltaic
conversion eciency was of 3.6% under simulated AM 1.5
sunlight.
150
Such an approach was similar to that carried out
with IL lling the straight nanopores of alumina sandwiched
between a counter electrode and a TiO
2
electrode.
151
Even
though the electrochemically inactive Al
2
O
3
wall occupies
50% of the electrolyte layer, the solar cell performances were
the same as those with IL gelled with Al
2
O
3
nanoparticles,
where random ion paths were expected. Actually, the increase
in performances was explained by straight ion diusion and
Gro tthuss-type diusions fabricated on Al
2
O
3
walls.
152
Similar devices based on ZnO nanoparticles and CNT layers
at the electrolyte interface (thus creating a good continuous
electrolytic junction) were tested.
153
Fully organic ionogel
electrolytes were also used, based on poly(vinylpyrrolidone),
and showed an overall light-to-electricity energy conversion
eciency of 5.41% under irradiation of AM 1.5.
154
Some
studies were reported with the same objective with organic
gelators, synthetic or natural, but the eciency was lower than
those already reported.
155,156
It is worth noting that previous
DSSCs based on volatile solvents showed the highest eciency
at 11%, but suered from intrinsic volatility. Replacement of
volatile solvents by ILs decreased eciency down to 7% and
showed long-time instability. However, the assemblies of
eutectic ternary mixtures of iodide ILs with nanocrystalline
TiO
2
particles at one of the DSSC interfaces led to eciency of
8.2% under AM 1.5 illumination.
157
It is remarkable for our
subject that association with oxide particles permitted to reach
high eciency as well as excellent stability, thus opening way
to low cost DSSCs.
Electrochemical sensors and biosensors. Coll et al. described
for the rst time the preparation of PVC membranes containing
[C
4
MIm][PF
6
] and polyazacycloalkane as ionophore for use as
anion-selective electrodes and found a remarkable selective
response to the highly hydrophilic anion sulfate.
158
Pletnev,
using the same concept, described the use of PMMA and PVC
membranes containing bis(triuoromethanesulfonimidate)
salts of 1-butyl-2,3-dimethylimidazolium and dodecylethyl-
diphenylphosphonium, [BDMIm][TFSI] and [DEDPP][TFSI],
respectively. These ion-selective membranes demonstrated
good and extremely stable responses to both cations and
anions (including surfactants).
159
Modied electrodes with bulky gels are characterized by a
large surface area, excellent chemical and physical stabilities
which make them ideal candidates for constructing sensors
with high performance. Zhu was able to selectively detect
dopamine even in the presence of ascorbic acid and uric acid
using a glassy carbon electrode modied with a MWCNTs/
[OMIm][PF
6
] gel.
160
An electrode modied with a gel
containing ferrocene lled with SWCNTs has been reported
which eciently catalyzed oxidation of H
2
O
2
to O
2
and
reduction to H
2
O.
161
ILs are known for their good biocompatibility with
biomolecules and enzymes and they improve their reusability
Fig. 11 All-solid dye sensitized solar cell. Reprinted with permission
from ref. 157.
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and stability. Thus, catalytically active proteins and enzymes
were also conned for biosensors applications in order to
achieve direct electron transfer.
162
Some examples are based
on the immobilization of enzyme-IL systems in chitosan
163
or
Naon
s
.
164
These membranes yielded suitable matrix for
direct electrochemistry of HRP and hemoglobin (Hb). New
hybrid organicinorganic siloxane-based hydrogels entrapping
IL have been recently developed for similar uses.
26
Interestingly, an amperometric biosensor was obtained by
coating the surface of a glassy carbon electrode with a
silica ionogel lm doped with HRP and ferrocene
(IL:[C
4
MIm][BF
4
]).
165
The resulting electrode had faster
response in sensing hydrogen peroxide than with classic
solgel lm, with a detection limit for H
2
O
2
of 1.1 mM. A
more sophisticated system based on silica/RTIL/Naon/
carbon electrode was described where Hb could be adsorb
onto the surface. This biosensor shows a stable, sensitive and
fast response to oxygen.
166
Bulky gels based electrodes can also be modied by
catalytically active proteins like Hb,
167
HRP
168
or glucose
oxidase.
169
Closely related works using carbon nanotubes
composites with gold
170
or AuPt nanoparticles
171
were also
reported.
Actuators. CNT nanollers are known to improve the
mechanical properties of polymers and to endow them with
electronic conductivity provided percolation threshold was
reached. In 2005 Aida et al. reported the synthesis of the rst
generation of bucky-gel actuators, which worked in air,
without any support or external electrolytes, and without
deposition of a metallic electrode layer. The lm was prepared
through layer-by-layer casting of the electrode from a mixture
of a uorinated copolymer (PVdF-HFP), 4-methyl-2-pentanone,
an IL and SWCNTs arising from high pressure COconversion.
172
However, the performances were limited by the robustness of
the polymer, which also lowered the electrical conductivity
and capacitance of the electrode layers. A second generation of
actuators was reported by the same authors in 2009.
173
These
actuators comprised polymer-free CNT electrodes obtained
using super-growth SWNTs arising from a water assisted
chemical vapour deposition. Performances were increased, so
that a displacement as large as 5 cm was observed at a
frequency of 1 Hz, that is a ten fold increase to the performance
of the rst generation. Recently, elastic conductors were
achieved from millimetre-long SWNTs, a uorinated copolymer
and a compatible IL, which could be made printable.
Conductivity of more than 100 S cm
1
and stretchability of
more than 100% were obtained. A rubber-like stretchable
active-matrix display that showed good luminance characteristics
was constructed from integrated printed elastic conductors,
organic transistors and organic light-emitting diodes.
174
5.2 Separation membranes
Besides their use as electrolytes, ILs are also well known for
their ability to dissolve a wide range of species, from organic
compounds to metal salts. The solubility of gases in ILs is of
prior importance for using them as solvents for reactions
(hydrogenation, hydroformylation etc.) or for the storage of
gases.
175
Emphasis was put on the outstanding ability to
dissolve carbon dioxide.
176
The use of ILs to separate gases
benets from huge advantages, as the absence of contamination
of the gas stream (in relation to the low vapour pressure of
ILs) and the possibility to work at higher temperatures than is
in conventional absorption solvents.
Actually, the specic properties of ILs considerably broaden
the range of separation applications, from metal ions
separations to chromatography. The design of task-specic
ions and the choice of the cationanion combination permit
one to tune the high or selective solvation ability and non
miscibility in water or other solvents. However, the challenge
to implement ILs in separation techniques is also to
develop supported IL membranes, either by immobilizing
ILs within polymer membranes or in porous inorganic
supports.
24
The operational stability of supported IL membranes based
on hydrophilic polymers has been demonstrated.
177
The
nature of the supporting polymer membrane strongly aected
the transport (i.e. permeation) rates and selectivity in the
separation of organics.
178,179
Ion selective polymer membranes
involving ILs (typically phosphonium salts) as ion exchangers
were successfully used in potentiometric sensors.
159,180
In
those cases, the hydrophobicity of the polymer (typically
PMMA or poly(vinyl chloride)) could prevent spontaneous,
non-specic ion extraction from the aqueous sample,
while the IL acted as a plasticizer, improving the solubility
and migration of analytes. The ability of ILs (typically
phosphonium based ILs like Cyphos 104) to extract metal
ions may nd application in ionogels as well. Some recent
examples include silica based ionogels for the extraction
of Y(III),
181
and alginate based ionogels for the extraction of
Pd(II).
182
In gas separation, ionogel polymer membranes were shown
to increase selectivity compared with conventional polymer
membranes (including those arising from polymerisable ILs).
However, the IL was likely to be displaced at low dierential
pressure. This problem was overcome by using a combination
of polymerisable IL with 20 mol% free RTILs to increase the
compatibility between the liquid and solid phase while keeping
good gas permeativity. These tailored membranes allowed gas
separation with a CO
2
permeability increased of B400%, and
an improvement of CO
2
/N
2
and CO
2
/CH
4
selectivity with
respect to analogous membranes arising from only poly-
merisable ILs.
183
It is worth stressing the ecient separation
of CO
2
from H
2
at temperatures around 100 1C and the topical
interest for applications as hydrogen production from syngas
(an industrial mixture of CO and H
2
which can be reacted with
water to produce CO
2
and more H
2
).
184
Another recent result
is the use of LMWG as 12-hydroxystearic acid to form gels
which exhibit liquid-like CO
2
gas transport ability as they are
composed of 98.5% of IL.
185
Hybrid organicinorganic membranes which involve the
dispersion of inorganic particles (typically zeolite) in the
polymer matrix combine superior selectivity with excellent
fabrication properties of polymer membranes.
186
However,
limited compatibility between inorganic and organic
components may result in a lack of adhesion. The addition
of IL both increased the permeability and proved to be an
excellent compatibilizer, yielding defect-free membranes.
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5.3 Catalytic membranes
SILC, where the IL (which contains the catalyst) is immobilized
as a thin lm on high surface area supports, has been widely
developed to circumvent viscosity and recyclability problems.
23,24
In this case, reactants and products diuse through the
residual voids in pores which are coated with the liquid
catalyst lm.
Silica based ionogels were shown to provide alternative
nanoreactors systems.
24
The presence of two interpenetrated
networks (silica and IL) allows free transport of reactants and
products through the liquid phase, while pore diameters are
small enough to prevent IL leaching. Actually, Deng et al.
reported the enhanced catalytic performance of the carbonylation
of aniline into ureas and carbamates in the presence of
ionogels loaded with Rh(PPh
3
)
3
Cl and Pd(PPh
3
)
2
Cl
2
.
89
The
reactions were carried out without additional organic solvent
in an autoclave at 135180 1C under 5 MPa CO pressure. Pd
salts were also encapsulated in silica based ionogels and apply
as an eective catalytic system without leaching for Heck
coupling reaction in the presence of toluene.
187
ILs have recently demonstrated attractive performances as a
reaction media in biocatalysis.
13
The activity of biomolecules
in ILs has been found to be comparable or higher than in
conventional solvents, and enhanced enzyme stability has been
reported. The rst reports of applications of ionogels to
biocatalysis seem promising. Thus, the activity of horseradish
peroxidase (HRP) immobilized in ionogels was shown to be
about 30-fold greater than that in silica gel without IL, with an
excellent thermal stability.
188
HRP was immobilized in iono-
gels prepared by acidic hydrolysis of TEOS in [C
4
MIm][BF
4
].
The enzyme was thought to be protected by the IL from the
detrimental eect of ethanol during the synthesis, while the
interconnected pore structure of ionogels would facilitate the
internal diusion of the substrate.
5.4 Drug release
Drug release has just emerged as a new application of ionogels.
It is dealt separately as, contrary to the previous elds of
applications, it is based on ionogels that are able to lose
gradually the IL. In other words, whereas all the other
applications require the complete stability of ionogels under
the operating conditions, drug release involves the in situ
delivery of the IL loading.
A common problem that exists with many active
pharmaceutical ingredients (APIs) is their low solubility. As
a result, much research is conducted on nding ways to
improve drug solubility and availability. It has been demon-
strated that ILs can dissolve compounds which are insoluble
or sparingly soluble in water and organic solvent including
cellulose and compounds having pharmaceutical activity.
These studied were however limited by the toxicological issue
of ILs. Some eorts have been conducted recently to obtain
nontoxic and biodegradable ILs.
189,190
Some ion constituents
of ILs have biologically activity, such as ammonium cations
which are well-known as antibacterial agents. Recently, new
ILs have been created from APIs, some of them combining
anionic and cationic APIs with biological activities that
complement each other. These new IL drugs present promising
advantages over usual solid APIs, which can suer from
polymorphic conversion, low solubility and low bioavailability
associated with the solid form.
Actually, the availability of APIs is a key issue. A tremendous
eort is currently being undertaken by the pharmaceutical
industry to develop drug delivery systems in which the release
of the active substance is controlled on demand. Drug
carriers being considered as promising candidates include
soluble polymers, microparticles made of insoluble or
biodegradable natural and synthetic polymers, microcapsules,
cells, lipoproteins, liposomes, and micelles. Silica matrices
show high biocompatibilitybiodegrability and resistance to
microbial attack and they exhibit higher mechanical strength,
enhanced thermal stability and negligible swelling in organic
solvents, compared to most organic polymers. All these
features make silica supports promising carriers for the drug
delivery systems formulation. Several research groups have
investigated both drug storage and delivery properties of
ordered mesoporous silica such as MCM-41 and SBA-15
and of solgel silica materials.
191
The use of ionogels for
biological applications is very limited to-date. Lin was the
rst to report on the synthesis of mesoporous materials
containing long alkyl chains antibacterial ILs and their use
as controlled release delivery device.
192
Recently some of us
reported the synthesis of a new IL containing drug composed
of an imidazolium cation and ibuprofenate anion.
193
We
succeeded in synthesizing new ionogels containing a high
amount of ibuprofenate by a simple one-step solgel procedure.
These ionogels were easily shaped and do not need any further
process to achieve a nal pharmaceutical form. The ibuprofen
release was found to be governed by the inner and the outer
surfaces of the ionogel, as well as the chemical nature of the
surface. More recently Goto et al. reported the use of
an IL-assisted microemulsion for transdermal delivery of
acyclovir using isopropyl myristate, Tween-80 as a surfactant
and span-20 as a co-surfactant.
194
Conclusions and prospects
Ionogels form a new class of hybrid materials which are just
emerging, but considerably increase the potential of ILs in
such key areas as energy, environment and analysis. Basically,
ILs are modularly tunable materials, on which, at least
potentially, the properties of both cation and anion components
can be independently modied. In ionogels, a further
dimension in this exibility space is oered by the unique
combinations of chemical and physical properties addressable
by their two-component nature. As shown in Fig. 12,
designing both the guest IL phase and the host support allows
the targeted synthesis of an ionogel which ts a specic task. It
is worth stressing that functionalization of ionogels can be
achieved by incorporation of organic functions in the host
matrix, by modifying the IL ions and by encapsulation of
functional molecules in the immobilized IL phase. In addition,
inherent tractability of polymer and particulate sols makes it
easy to shape ionogels in dierent geometries and laminated
structures adapted to a specic device.
However, the properties of the nal ionogel as a
hostguest material are dierent from the simple combination
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(or hybridation) of those of each pure component. Actually,
the concept of ionogel involves a fascinating chain of nano-
structuring interactions (Fig. 13), from the supramolecular
structuring ability of ILs in the synthesis of solids, to the
connement eects occurring in these solids used as host
matrices, which in turn inuences the nanostructure of the
guest IL.
Typically many ionogels can be seen as two continuous
interpenetrated networks of solid and liquid (i.e. two continuous
percolation pathways). Classical structuring process involves
a phase separation induced by the (organic or inorganic)
polymerization. This (spinodal type) phase separation results
in the formation of two interpenetrated nanophases, which
accordingly causes an increase of interface. This phenomenon
takes place before the thermodynamic phase separation which
conversely tends to minimize the interface energy. To be
eective, such structuring process then implies that the gelation
freezes the transient bi-continuous structure before the
system spontaneously evolves to macroscopic phase separation.
Thus, ionogels can be structured at the nanometre scale by
playing on the compatibility of the IL with the polymer or the
inorganic phases that grow up during the in situ synthesis. This
compatibility can be tuned by combining the choice of the
cationanion pair and the tools of macromolecular chemistry
(modication of polymer chains, synthesis of block co-polymers)
and solgel chemistry (use of silicon precursors bearing
organic groups).
However, once the IL is immobilized in the host matrix (e.g.
polymer or silica), its nanostructure and physicochemical
properties may be in turn aected. Typically this has been
illustrated by some reports of connement eects in some
inorganic ionogels. These eects are strongly related to the
pore size and depend on the nature of both the IL and
the matrix. They appear to be limited to a modication of
the short-range organization and molecular dynamics at the
close neighbourhood of the pore wall. Most physicochemical
properties are not markedly changed by the connement in
mesopores. This is roughly the case of ionic conductivity. A
salient feature of ionogels is that the IL keeps a liquid
behaviour on connement. Anyway, some drastic modications
have been reported as the disappearance of phase transitions
or the appearance of new ones, or the striking enhancement in
luminescence emission of dicyanamide anion.
Finally, if one keeps in mind that over the last decades the
use of ILs have evolved from electrochemical and general
solvents to catalysts, lubricants, thermal uids, magnetic
uids, optical uids, propellants, active pharmaceutical
ingredients etc., one feels that the concept of ionogel opens
unlimited possibilities of applications and should inspire
innovative, and likely unexpected, developments in future
technologies.
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) that formed are weaker bases than the

), because of solvation by the additional

), using the NernstEinstein equation,

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