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org/ees | Energy & Environmental Science

Energy applications of ionic liquids


James F. Wishart*
Received 30th March 2009, Accepted 1st May 2009
First published as an Advance Article on the web 11th May 2009
DOI: 10.1039/b906273d

Due to their unusual sets of properties, ionic liquids have many important applications in devices and
processes for the production, storage and efficient use of energy and other resources.

Introduction
Ionic liquids (ILs) are defined (somewhat arbitrarily) as molten
salts whose fusion temperatures are at or below 100  C. Although
their history extends back almost a century,1 they have received
a burgeoning amount of attention in the present decade. While it
may have been tempting a few years ago to view the interest in
the field as a passing fad, the literature on ionic liquids continues
to grow rapidly and to diversify into new areas. Ionic liquids are Fig. 1 Typical cations and anions used to make ionic liquids.
here to stay.1
The attraction of ionic liquids (ILs) lies in their remarkable set
of properties when compared to conventional solvents. As salts them combustion resistant, evaporation-proof, and suitable for
consisting of distinct anions and cations, ILs are inherently vacuum applications, and the lack of a boiling point (below the
binary (or higher order) systems. The anions and cations can be decomposition temperature) means that many ILs have very
independently selected to tune the IL’s physicochemical prop- wide temperature ranges in the liquid state. In some ILs the fluid
erties (melting point, conductivity, viscosity, density, refractive range extends all the way down to the glass transition tempera-
index, etc.) while at the same time introducing specific features ture (typically 110 to 50  C). On the other hand, certain ILs
for a given application (hydrophobicity vs. hydrophilicity, can be distilled if they are heated in high vacuum,2 or, as in the
controlling solute solubility, adding functional groups for case of protic ionic liquids, they are in equilibrium with volatile
catalysis/reactivity purposes, chirality, etc.) Examples of typical neutral molecules via a proton transfer reaction.3
IL anions and cations are shown in Fig. 1, however these are only Ionic liquids are intrinsically conductive since they typically
a sample of the infinite variety available. Generally speaking, contain on the order of 2–5 M electrolyte, however the viscosities
various tricks, such as using bulky organic ions, fluorous of ionic liquids tend to be higher than conventional solvents,
substitution, and low-symmetry structures, are employed to ranging from 20–30000 cP at room temperature. Nevertheless,
prevent efficient ion lattice packing that would result in strong low-viscosity ionic liquids often have room-temperature
coulombic interactions and high-melting solids instead of room- conductivities of 1–10 mS cm 1, comparable to or larger than
temperature liquids. that of 0.1 M aqueous KCl solution. The reciprocal relationship
Although the coulombic interactions in ILs are weakened by between the viscosities and conductivities of ionic liquids, and
design, in most cases they remain strong enough to make the IL’s causes of non-ideality, have been carefully studied by Angell and
vapour pressure negligible at room temperature. Herein lies one coworkers,4 as well as other groups.5
of the major distinctions of ILs – the low vapour pressure makes A large fraction of the reported ionic liquids are amphiphilic
due to the hydrocarbon side chains that festoon the cations or
anions. Molecular dynamics simulations6 have shown that
Chemistry Department, Brookhaven National Laboratory, Upton, NY,
11973, USA. E-mail: wishart@bnl.gov; Fax: +1 631 344-5815; Tel: +1
hydrophobic domains can be formed through hydrocarbon side-
631 344-4327 chain aggregation, and if the chains are long enough the domains

Broader context
During the early phases of the rapid growth of interest in ionic liquids, their ‘‘green’’ and environmentally-friendly characteristics
were praised perhaps a little too enthusiastically. Ionic liquids, like any materials, are not intrinsically green; their environmental
benefits accrue through the ways they are employed. As our understanding of ionic liquids and their novel combinations of tunable
properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable production, storage
and efficient use of energy as components of advanced devices and processes. This brief review provides a basic introduction to ionic
liquids and their interesting properties, and enumerates how these properties are being applied to improve the ways in which we
generate, store, and consume energy.

956 | Energy Environ. Sci., 2009, 2, 956–961 This journal is ª The Royal Society of Chemistry 2009
can merge into a continuous structure within the IL interwoven dye-sensitized solar cells (DSSCs).11 DSSCs use a metal complex
with the polar domain. This results in the second major distinc- or organic dye absorbed onto a semiconductor, such as TiO2,
tion between ILs and molecular solvents – their ability to dissolve which has been applied to an electrode. Capture of a photon by
and solubilize a wide range of polar and nonpolar materials that the dye causes the excited state to inject an electron into the TiO2.
would not be simultaneously soluble in a conventional molecular The oxidized dye is reduced by a charge carrier within the elec-
solvent. Solutes can range from inorganic salts to hydrocarbons, trolyte, typically iodide anion. The electron and the oxidized
synthetic and bio-polymers, lipids, sugars, proteins and even species (‘‘hole’’) recombine at the counter electrode, completing
functional enzymes. ILs can dissolve wood and lignocellulosic the circuit.
materials,7 and they even show promise as less hazardous fixa- Although ILs are conductive, mass transport of the hole
tives for embalming tissues.8 carrier to the counter electrode can be a limiting factor for IL
Due to the electrostatic constraints of this ionic fluid, the polar DSSC performance.12 Iodide is the most utilized hole carrier
and nonpolar regions are forced to remain in intimate contact because I0 can dimerize to form I2 and pick up an iodide anion to
and the liquid is heterogeneous on the molecular scale. Concepts form I3 . A Grotthus-type exchange mechanism transferring I2
of polarity that are useful for understanding the nature of between I3 and I has been invoked to explain the superior
conventional solvents are ill-defined in ionic liquids.9 Empirical charge transport in iodide-based DSSCs.13 A large body of
polarity measurements often give conflicting results, since probe literature traces the improvement of IL-based DSSCs. The
molecules sample local environments to which they have the present state of the art employs mixtures of IL cations and anions
highest affinity, recalling the Indian fable of the blind men and (in addition to I and I3 ) to lower viscosity and thus optimize
the elephant. Long-range structural order can persist in ionic hole transport. The energy efficiencies of IL-based DSSCs are
liquids as well, for example interfacial layering at charged close to those of the best conventional solvent-based systems,
surfaces.10 These features can give rise to new reactivity patterns, with substantial improvements in durability.14
the preparation of hybrid materials, and the fabrication of
advanced devices.
Solar thermal conversion
The introduction above provides only a brief overview of the
features of ionic liquids that motivate their energy-related Another emerging technology for conversion of solar energy
applications. Their utility manifests itself in wide-ranging aspects involves using arrays of reflectors to focus sunlight onto vessels
of energy production, storage and utilization. or pipes containing a heat transfer fluid. The heated fluid is then
conducted through a system that converts the heat into elec-
Ionic liquids and energy production tricity, either through thermoelectric conversion or by powering
a generator. The heated fluid can be stored in an insulated vessel
Ionic liquids will play many roles in the production of energy, for for electric generation on demand. Fluids for these systems must
example in the capture and conversion of solar energy into endure a wide range of temperatures, from night-time lows in
electricity, the conversion of raw biomass or fossil resources winter to daytime operating temperatures in excess of 200  C.
into cleaner fuels, and enabling advanced nuclear energy Many ILs are liquid and stable over that entire range, and several
technologies. studies15 have supported their suitability for this application. In
addition to large-scale electricity installations, the technology is
Solar photoconversion being investigated to provide direct heat and air conditioning to
hospitals and resorts in Mediterranean countries.16
Due to their conductivity, low volatility, and thermal stability,
ionic liquids have been extensively studied as electrolytes for
Biofuel production
Biofuels such as ethanol, butanol and biodiesel represent
a potentially sustainable, carbon-neutral transportation fuel
James F. Wishart received a BS source if they can be obtained from non-food biomass grown and
in Chemistry from the Massa- harvested in an ecologically stable manner. One of the biggest
chusetts Institute of Technology challenges is that the bulk of the energy available from such
in 1979 and a PhD in Inorganic biomass (corn stalks, switchgrass, softwood, etc.) is in the form
Chemistry from Stanford of lignocellulose, a tight, covalent- and hydrogen bond-linked
University in 1985 under the matrix of the carbohydrate polymers cellulose and hemicellulose
direction of Prof. Henry Taube. and the phenolic polymer lignin. Plants owe their sturdiness to
After a postdoctoral appointment the durability of lignocellulose and its ‘‘recalcitrance’’ to chemical
at Rutgers University he joined and biological attack. Breaking down lignocellulose into its
the Brookhaven National Labo- components so that they can be converted to biofuels requires
ratory Chemistry Department in harsh chemical treatments or specialized organisms (e.g., fungi).
1987. His research interests Happily, ionic liquids that have anions with good hydrogen
include ionic liquids, radiation bond accepting properties, such as Cl , carboxylates, and
James F: Wishart chemistry, electron transfer, and oxoanions, can dissolve cellulose (and lignocellulose) by dis-
new technology and techniques rupting their networks of intramolecular hydrogen bonds.17 It is
for pulse radiolysis. therefore possible to dissolve wood and other plant material.7,18

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The dissolved cellulose (or lignocellulose) can be recovered by international recognition32 of the urgent need to reduce CO2
addition of water to the ionic liquid. The water breaks up the emissions calls for the growth of nuclear power generation in the
cellulose–anion hydrogen bonds and precipitates the cellulose in near term to avoid an even larger increase in greenhouse gases
a structurally disrupted form that is easier for enzymes to cleave from fossil fuel-based generating stations. Still, serious technical
into fermentable sugars to make ethanol, for example.19 Several and political problems persist in the handling and ultimate
groups are working on the adaptation of ionic liquid pre-treat- disposal of spent nuclear fuel and waste. Current approaches are
ment of biomass for the production of ethanol and butanol. Ionic not sufficient for future needs, and work is underway to design an
liquids could possibly be used to extract butanol out of dilute advanced fuel cycle33 that recycles spent nuclear fuel to signifi-
aqueous fermentation broths.20 cantly minimize waste, extracts more energy from existing
Ionic liquids have been used to solubilize other natural uranium supplies, and burns up plutonium and other transuranic
biopolymers in addition to cellulose, such as silk21 and wool elements so that they are no longer weapons proliferation risks
keratin,22 and to make hybrid biopolymer materials with exotic nor hazards to future generations.
items such as magnetic nanoparticles23 and carbon nanotubes.24 Such a sea change in technology requires the development of
ILs have enabled the exploitation of cheap, renewable biopoly- new, detailed spent fuel treatment and separations schemes that
mers in many applications that used to be the province of fossil present many challenges for chemists. Ionic liquids can play key
fuel-derived plastics. roles in advanced fuel separations systems because of their useful
Biodiesel is another alternative fuel that has received a lot of properties, including low volatility and combustibility, amphi-
attention because of its compatibility with the present trans- philicity, tuneable separations affinities including functionaliza-
portation infrastructure. Several groups have used ionic liquids tion, high conductivity, wide liquidus range and high thermal
to convert triglycerides to glycerol and biodiesel (fatty acid stability. In addition, ionic liquids containing boron can
methyl esters) through transesterification by immobilized lipase25 dramatically reduce the risk of criticality accidents in the pro-
or homogeneous catalysis.26 cessing of fissile materials.34 Several groups are investigating the
liquid/liquid extraction behaviour of ionic liquids for actinides
and fission products (lanthanides, Cs, Sr, Tc, etc.).35 Binnemans
More efficient production of cleaner fossil fuels
recently published a review on lanthanides and actinides in ILs.36
Although alternative energy sources will increase in capacity over ILs have been shown to be effective solvents for extraction, but in
time, fossil fuels will remain a major source of energy for the some cases the operative mechanism is ion exchange instead of
foreseeable future. Ionic liquids can make their production and true neutral extraction.37 Several studies have revealed the effect
use cleaner. Desulfurization of petroleum feedstocks is vitally of IL anion and cation hydrophobicity on the balance between
important for the prevention of air pollution via SOx aerosols the mechanisms.38 In addition to liquid/liquid extraction, various
and the environmental destruction caused by acid rain, as well as elements can be selectively electrodeposited in metallic form,
for the protection of antipollution catalysts and fuel cells. Stan- even if highly reactive, due to the high conductivity and wide
dard methods such as hydrodesulfurization require elevated electrochemical windows of selected ILs.39 The use of ionic
temperatures and pressures, along with hydrogen gas. liquids to electrodeposit a wide variety of metals and alloys has
Ionic liquids have been shown to be effective at extracting industrial and commercial applications far beyond the nuclear
sulfur compounds from fuels under ambient conditions, field.40,41
including compounds that are difficult to remove through Instability under the radiation burden of spent nuclear fuel is
hydrogenation such as dibenzothiophene.27 Ionic liquid extrac- a common problem for nuclear separations systems based on
tion has been coupled with oxidation by H2O2 to boost effi- conventional solvents. Therefore it is important to understand
ciency,28 in some cases catalyzed by polyoxometallates.29 Ionic the chemistry produced by irradiation of ionic liquids and its
liquids containing Lewis acidic metal complex anions also show potential effects on separations processes. A review of this issue
high performance.30 has recently been published.42 Ionic liquid radiolysis product
Ionic liquids are also effective for extracting aromatic hydro- studies have shown that ILs are generally resistant to radiation
carbons from aromatic/aliphatic mixtures, and an engineering damage, and product distributions have been characterized.43
analysis has shown significant cost savings and process benefits EPR identification of radiation-induced radical species relates
could be obtained by ionic liquid-based removal of aromatics initial transient species to the ultimate product distributions.44,45
from naphtha cracker feed streams.31 Regardless of the ability of Unlike conventional hydrocarbon solvents that direct damage
ILs to extract organic materials out of hydrocarbons, they show into the extractant molecules, thus reducing their efficiency, ionic
limited solubility in hydrocarbons for the same Coulombic liquids can be designed to direct damage away from the extrac-
reasons that make their vapour pressure very low. Consequently, tant, thereby increasing the durability of the separations
they are not washed away, even over many process cycles, system.42,44 There are numerous reasons to believe that the future
a bonus for their cost efficiency. of ionic liquids in advanced nuclear fuel recycling is bright.

A cleaner, advanced nuclear fuel cycle


Ionic liquids and energy storage
Nuclear power provides a significant fraction of the world’s
Batteries and supercapacitors
energy, and it is a major carbon-free source of continuous, base-
supply electrical power generation. Although the proportion of The strongest motivation for the development of ionic liquids in
renewable alternative energy production will continue to grow, the early years of the field was in their use as battery electrolytes,

958 | Energy Environ. Sci., 2009, 2, 956–961 This journal is ª The Royal Society of Chemistry 2009
where their conductivity, wide electrochemical windows and chemical inertness and low volatility promise gains in reliability
liquidus ranges, and low volatility made them attractive for high and useful lifetime. In addition to changing color, the charging or
performance applications such as thermally-activated batteries.46 discharging of conductive polymers can be coupled to IL ion
The electrochemical properties of ionic liquids are intensively migration and electrostriction to produce physical displace-
studied worldwide and several reviews47–50 and books41 have been ments, creating electromechanical actuators or ‘‘artificial
published on the subject, which includes many uses of ILs that muscles’’.48,49,57 Turning signal transduction in the opposite
fall under other sections of this minireview. The field is so large direction, ILs can be used to make sensors for the electro-
that it is not possible to do it justice within this space; interested chemical detection of gases, ions (selective electrodes), biomole-
parties are urged to consult the reviews. cules, and electroactive species.58 Similarly, the principles used to
Ionic liquids have been studied in nearly every battery system design IL-based actuators could be applied to portable energy
imaginable, but their use in lithium batteries has received the harvesting systems59
greatest attention.47–49,51 Because of their chemical and
thermal stability, ILs are a good choice for development of Catalysis and industrial applications
batteries with lithium metal anodes, although there are issues
with film formation at the IL/Li interface that require further The use of ionic liquids in catalytic systems has been studied
investigation. extensively1,60 Because many ILs are practically insoluble in
Supercapacitors store energy through the formation of elec- hydrocarbons and supercritical CO2,61 particular attention has
trochemical double layers formed by the adsorption of ionic been paid to their use in phase-transfer catalysis, particularly
species on electrode surfaces.47,49,52 They are designed to have when the catalyst can be ‘‘immobilized’’ in the IL (to prevent
very large electrode surface areas and they can store much more its loss and product contamination) by attaching a charged
charge than conventional dielectric capacitors. They can be functionality.
charged and discharged rapidly, and thus have higher power The solubility of gases in ionic liquids and their general lack of
densities than batteries, although their energy density is lower. volatility make them useful for gas capture or separation appli-
Supercapacitors have many uses in mobile electrical systems and cations, for example using supported ionic liquid polymer
power distribution systems (regenerative braking, accelerating membranes for separation of CO2, SO2, etc.,62 H2 purification63
electric vehicles, load buffering, uninterruptible power supplies) and storage of large gas volumes under mild conditions.64
that can markedly improve energy conservation. Supercapacitors
can also enhance the performance characteristics of batteries
Conclusion
and fuel cells. Because of the ionic nature, conductivity and
durability of ILs, supercapacitors using them are actively being Well over a dozen edited books, at least 14,000 articles, and
developed.47,49,52,53 hundreds of patents concerning ionic liquids have been written.
This short minireview highlights the major ways that ILs can
Ionic liquids and efficient energy utilization impact energy technologies from generation to consumption.
Most of the examples mentioned are still in the research and
Ionic liquids impact energy utilization most directly through development stage, but commercial application of ILs continues
their application to fuel cells, but there are many other ways that to move forward in many areas. It is hoped that this brief
they can make positive contributions indirectly through introduction to ionic liquids will inspire new ideas for IL uses
improved materials, devices and processes that conserve energy among the readers of this review.
or other resources during their manufacture or operation. The
example of metal electrodeposition has already been mentioned
above. Acknowledgements
This work was supported by the U. S. Department of Energy,
Fuel cells Office of Basic Energy Sciences, Division of Chemical Sciences
As low-volatility conductive media with good thermal stability, under contract # DE-AC02-98CH10886.
ionic liquids are finding applications as fuel cell electrolytes and
as proton conductors in proton exchange membranes, often in
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