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PERSPECTIVE

Lithium-ion batteries. A look into the future

Bruno Scrosati,*ab Jusef Hassounab and Yang-Kook Sun*b
Received 1st April 2011, Accepted 9th June 2011 DOI: 10.1039/c1ee01388b
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A critical overview of the latest developments in the lithium ion batteries technology is reported. We rst describe the evolution in the electrolyte area with particular attention to ionic liquids, discussing the expected application of these room temperature molten salts and listing the issues that still prevent their practical implementation. The attention is then focused on the electrode materials presently considered the most promising for enhancing the energy density of the batteries. At the anode side a discussion is provided on the status of development of high capacity tin and silicon lithium alloys. We show that the morphology that is the most likely to ensure commercial exploitation of these alloy electrodes is that involving carbon-based nanocomposites. We nally touch on super-high-capacity batteries, discussing the key cases of lithium-sulfur and lithium-air and attempting to forecast their chances to eventually reach the status of practically appealing energy storage systems. We conclude with a brief reection on the amount of lithium reserves in view of its large use in the case of global conversion from gasoline-powered cars to hybrid and electric cars.

1. Does the actual lithium battery technology comply with the electric road transportation criteria?
Our present energy policy, still mainly based on burning fossil fuels, inevitably poses a serious concern due to CO2-related global warming. Accordingly, efforts aimed at ensuring efcient use of renewable energy sources and replacement of internal combustion engines with electric motors for the development of
a Department of Chemistry, University of Rome Sapienza, Piazzale Aldo Moro, 5, 00185 Rome, Italy. E-mail: bruno.scrosati@uniroma1.it; Fax: +39 06 491769; Tel: +39 06 4991 3530; jusef.hassoun@uniroma1.it; +39 06 4991 3664 b Department of WCU Energy Engineering and Chemical Engineering, Hanyang University, Seoul, 133-791, Korea. E-mail: yksun@hanyang.ac. kr; Fax: +2 2282-7329; Tel: +2 2220-0524

sustainable vehicles, such as hybrid vehicles (HEVs), plug-in hybrid vehicles (PHEVs) and ultimately, full electric vehicles (EVs), are in progress worldwide. Exploitation of alternative, green, energy sources (solar, wind, geothermal) requires the side support of energy storage systems that can compensate their intermittent characteristics. It is now generally accepted that among the various possible choices, the most suitable are electrochemical batteries. Batteries are portable devices capable of delivering the stored chemical energy as electrical energy with high conversion efciency and without any gaseous emission. Moreover, batteries offer the most promising option to power efciently HEVs or EVs. In this scenario, particularly appealing are rechargeable batteries beneting from high specic energy (high voltage joined with high specic capacity), high rate capability, high safety and low cost.

Broader context
In this review, we discuss the new trends in the lithium battery R & D aimed at the development of advanced systems beneting of safety and energy levels higher than those offered by the present technology. Considering that steps forward may be marked only by renewing the chemistry of the battery, we discuss the approaches under evaluation for upgrading anode, electrolyte and cathode. At the anode side, much attention is presently devoted to lithium metal alloys, such as Li4.4Sn and Li4.4Si, since they offer specic capacity values much higher than conventional graphite. We discuss the properties of these alloys and show that their electrochemical response may be properly achieved by moving to special morphological congurations and, in particular, to carbon nanocomposites. Electrolyte systems more reliable and stable than the present liquid organic carbonate solutions are also of key importance for the progress of lithium battery technology. Good candidates are solutions of lithium salts in ionic liquids; accordingly the properties of these solutions and their practical prospects are discussed. Finally, we examine the use of high capacity cathode materials, such as sulfur and oxygen, in view of their utilization for the development of lithium super-batteries capable of offering energy densities three or four times higher than the common lithium-ion batteries.
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Promising candidates are Li-ion batteries that today exceed at least by a factor of 2.5 any competing technology thanks to the high value of energy density, i.e. 150 Whkg1 and 650 Whl1.1 Due to their unique features, lithium-ion batteries are the power sources of choice for the portable electronic market (including popular products such as cellular phone, laptop computers, mp3s, etc), are aggressively entering the power tool equipment market and, in particular, the emerging sustainable vehicle market.2 However, the present Li-ion batteries, although a commercial reality, are not yet at such technological level as to meet the requirements of efcient hybrid or electric vehicles. Reduction in cost, enhancement in safety and, especially, improvement in energy density, are mandatory requirements Conventional Li-ion batteries rely on a graphite anode, a lithium cobalt oxide cathode and liquid, organic carbonate electrolytes.3 At extreme operational conditions, such as at the upper limit of the charge process, oxygen may be released from the layered LiCoO2 cathode and, in the event of local overheating, it may react with the ammable organic liquid electrolyte, giving rise to thermal runaway effects, if not even to explosions. Various re incidents have been in fact reported during battery manufacturing and/or for battery-operated devices. Considering their very

Fig. 1 Ionic liquids are room temperature molten salts formed by the combination of a weakly interacting, large cation, e.g. of imidazole type and a exible anion, e.g. N,N-bis(triuoromethane sulphonyl) imide, TFSI.

Bruno Scrosati is Senior Professor of Electrochemistry at the University of Rome. He received the title of Doctor in Science honoris causa from the University of St. Andrews in Scotland and the honorary doctor degree from Chalmers University of Technology in Sweden. He was President of the Italian Chemical Society and of the Electrochemical Society. He is European Editor of the Bruno Scrosati Journal of Power Sources and member of the Editorial Boards of various other international journals. Bruno Scrosati is author of more 450 publications; 30 books and chapters in books and 22 patents. His H factor is 43.

limited number in respect to the level of production (a few hundred cases versus billions of cells per year), these incidents have not considerably affected the consumer electronic market; however, they cannot be tolerated in the vehicle market: a re in a battery-powered car would be very delecterious, if not fatal, for the success of the entire electric transportation business. Hence, full safety achievement is a mandatory goal for Li-ion batteries directed to HEV or EV use. This is not an easy task. The substitution of LiCoO2 with a chemically more stable material, e.g. olivine LiFePO4 (the PO4 group has stronger covalent bonds than the CoO2 one) is not a nal solution, due to the reactivity of the other components and, in particular, the instability and ammability of the liquid organic electrolyte.

2. Ionic liquids: exciting, safe electrolyte media for advanced batteries

Much attention is presently devoted to the investigation of electrolyte systems more reliable and stable than the present liquid organic carbonate solutions. Yang-Kook Sun obtained his PhD from Seoul National University, Republic of Korea, and is now a Professor of Energy Engineering at Hanyang University. His research interests include metaluoridecoated cathodes, lithium transition metal oxides, olivine-related cathodes and core-shell with concentration-gradient materials for advanced lithium ion ies, and lithium-metal-free lithium sulfur and lithium air batteries.

After graduating in Chemistry, Jusef Hassoun worked in a company for 3 years before returning to the University of Rome La Sapienza to obtain the PhD degree in Material Science in the eld of advanced lithium ion batteries. He is currently a Postdoctoral Researcher and has more than 40 publications in international journals.
Jusef Hassoun Yang-Kook Sun

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Particularly promising are solutions of lithium salts in ionic liquids. Ionic liquids (ILs) are room temperature molten salts formed by the combination of large organic cations (e.g. imidazolium or pyrrolidinium cations) and high-charge delocalized anions (e.g., N,N- iso(triuoromethane)sulfonimide (TFSI) anion),4 see Fig. 1. The basic science and electrochemical characteristics of ILs are widely reported and discussed in comprehensive reviews4 to which the reader is referred for details. Indeed, ILs are characterized by many favourable features, including high conductivity, environmental compatibility and, especially, high thermal stability.4 In contrast to organic carbonate solutions that catch re very easily, IL-based solutions are not ammable and generally stable up to 300400  C. In addition, ILs are basically composed of organic ions which may undergo almost unlimited structural variations because of the easy preparation of a large variety of their components and this provides a unique source of materials that can be designed and selected to full the requests of any desired device.5 Considering these features, ILs are in principle very appealing lithium ion battery electrolytes. Effectively, ILs are presently under testing in many industrial and academic laboratories with the aim of establishing their practical feasibility.69 However, the route to implementation of these systems is still a long one. A lot remains to be done before ionic liquid-based solutions can nd their successful application as practical lithium ion battery electrolytes. Many basic aspects are yet to be claried. For instance, the structure of the IL/electrode interface is still unknown despite the fact that its full understanding is of key importance in view of battery applications.4 In addition, IL-based solutions are apparently not stable at low, reducing voltages, e.g., when in contact with highly negative electrodes, such as lithium metal and/or graphite anodes. There is still a debate on whether this instability has to be assigned to reduction of liable groups in the IL cations structure and/or, more simply, to residual impurities. Therefore, there is an urgent need to devote more attention to these aspects by carrying out a series of systematic studies on the fundamental processes occurring at the solid electrodeionic liquid interface. Both experimental (e.g., detailed and systematic AC impedance studies) and theoretical (e.g. computing models) approaches may be appropriate for reaching the goal of shedding some light on the basic electrochemistry of ionic liquids.

3. The challenge of practical implementation of super capacity tin and silicon lithium alloys
Another key requirement for ensuring protable use of Li-ion batteries in electric vehicles is an increase in energy density. It may be estimated that for ensuring a 150 km driving range with a single charge for a common, sub-compact passenger car, the weight of the battery, if based on presently available Li-ion technology having an average energy density of 150 Whkg1, would be over 160 kg, this largely exceeding any practically acceptable limit. Clearly, advanced batteries, having levels of energy density two or three times higher than those offered by conventional systems, are urgently needed. The achievement of this goal requires the development of electrode materials having a much higher specic capacity than the conventional ones, still maintaining the same voltage levels.
This journal is The Royal Society of Chemistry 2011

With this in mind, a lot of attention is presently devoted to tin and silicon, since they are abundant (cheap), environmentally benign and, most importantly, their alloys with lithium, i.e., Li4.4Sn and Li4.4Si, offer specic capacity values much higher than conventional graphite, namely 990 mAhg1 and 4200 mAhg1, respectively, versus 370 mAhg1. The potentialities of these materials have been known for some time10,11 but their exploitation has been until recently prevented by a serious issue associated with large volume expansion-contraction changes experienced during the lithium alloying-de-alloying electrochemical process that in turn induce cracks and, eventually, pulverization of the electrode, nally leading it to dying in the round of a few cycles. The advent of nanotechnology has helped to control this issue. In fact, by reducing the metal particle size to a nanometric level, the volume change may be controlled and the lithium diffusion length greatly reduced, thus improving the performance of the electrode in terms of both life and rate capability.12,13 Nanostructured electrodes are not, however, practically feasible since their large surface area reects on high reactivity and on reduction of tap density, with associated increase in safety hazard and decrease in volumetric energy density. All these aspects are discussed in detail in recent and comprehensive reviews12,13 to which the reader is referred for more comprehensive information. The breakthrough in this eld has been achieved by the development of cleverly designed carbon-metal composites. By an oversimplied way, these composites may be described as formed by low-size metal particles dispersed within a carbon matrix. The carbon matrix, while maintaining in its core the nano sized metal particle conguration that helps in containing the volume stress, supplies an overall compact structure which ensures stability and provides high tap density. It is now widely assumed that the nanocomposite approach is the most promising one to lead to electrode materials having practical relevance. The validity of this assumption and of the nanocomposite concept is supported by two convincing experimental examples. One is given by the tincarbon, SnC composite, the morphology of which is shown in the TEM images of Fig. 2.14 The images clearly show that the tin particles are kept at nano size dimensions (about 1030 nm) and that they are evenly dispersed within the carbon matrix. The latter has a two-fold, critical action, namely it provides enough free volume to accommodate the tins expansioncontraction, this ensuring cycling stability, and, at the same time, acts as a protecting shell,

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Fig. 2 TEM images of a SnC composite (a) and of a single Sn particle (b). Taken from ref. 14 with permission from Wiley-VCH STM Copyright.

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delivered specic capacity is depressed with respect to that associated with pure tin, namely about 500 mAhg1 versus 990 mAhg1, due to the weight contribution from the carbon matrix that is 50% in the case of the SnC composite here discussed. This penalty in capacity is largely counterbalanced by the excellent electrochemical response of the composite. Note that the capacity delivered by the composite electrode is still much higher than that obtainable by a conventional graphite anode. Fig. 3b, which reports in situ XRD analysis of the Li/Sn-C cell at its pristine state and after a full chargedischarge cycle,15 demonstrates that the electrochemical lithium alloyingdealloying process is fully accomplished and this further conrms the reversibility of the electrode. Finally, Fig. 3c shows the time evolution of the XRD patterns of a SnC composite sample kept in open air at room temperature for over a month. No evidence of peak modication nor appearance of peaks related to tin oxide was detected after long air exposure or even after heat treatment.14 This result demonstrates the stability of the composite, which in turn reects in easy handling, a very important advantage in view of practical applications. The interest in LiSi alloys is even larger than that in LiSn alloys and this is understandable considering that the former offers the highest theoretical specic capacity so far known for lithium battery electrode materials. The volume stress issue, already discussed for tin, also holds for silicon, possibly even at a higher extent. Indeed, the volume change expected for silicon upon full alloying with lithium to form Li4.4Si is of the order of 300% while that for tin at the same Li4.4Sn composition is about 250%. Therefore, similar to the tin case, extensive work has been devoted in the last few years to the design of electrode congurations capable of buffering the volume changes such as to make also the silicon electrode viable for practical applications.

Fig. 3 Characteristics of a SnC composite electrode. (a) Capacity versus cycle number in a lithium cell; (b) in situ XRD analysis of a Li/Sn-C cell from its pristine state and after a full chargedischarge cycle; (c) XRD evolution of SnC composite powder exposed to ambient atmosphere. Taken from ref. 14 and 15 with permission from Wiley Wiley-VCH STM Copyright.

this warranting chemical stability and safe handling of the electrode. The above two benecial actions are clearly demonstrated by Fig. 3. Fig. 3a shows how the composite can be efciently cycled in a lithium cell with a charge (lithium-tin alloying process: SnC + 4.4Li / L4.4Sn + C) - discharge (lithium-tin de-alloying process: L4.4Sn + C / SnC + 4.4Li) coloumbic efciency approaching 100%. The long and stable cycle life combined with high efciency is a very convincing evidence that indeed the volume stress is here successfully buffered. Obviously, the
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Fig. 4 Morphological and electrochemical characteristics of a SiC composite. (a) SEM image of the composite particles; (b) cross-section SEM image of a composite sphere; (c) high resolution TEM image of the composite; (d) chargedischarge cycle of the SiC composite in a lithium cell. Courtesy of Prof. Lee from Kangwon National University, South Korea, taken from ref. 21 with permission from Elsevier (license # 2647500596262).

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Morphological modications aimed at developing nanometric structures, such as nano-sized particles,16 sub-micrometric pillars17 and nanowires18 led only to limited improvement in terms of cycle life. Beside, some of these morphologies, e.g., silicon nanowires, are dangerous for the human health. Some advancements have been obtained by using methyl cellulose CMC as a binder for the Si electrode blend19 and by exploiting 3D porous Si particle conguration.20 However the cycle capability and the tap density of these electrodes are both low, this resulting in a limited life and modest volumetric energy density, respectively. As in the case of tin, also for silicon the real breakthrough can arrive with the development of appropriate carbon composites. Illustrative in this respect is the case of a recently developed spherical silicongraphitecarbon composite.21 The morphology of this material and its electrochemical response in a lithium cell are illustrated in Fig. 4. We can see that the composite is formed of spherical Si particles of 30 nm average size, surrounded by amorphous carbon that may act as a buffering agent to account for the volume stress (Fig. 4ac). This particular conguration is benecial in terms of optimization of the electrochemical response: in fact, Fig. 4c which illustrates a typical chargedischarge cycle of the composite electrode in a lithium cell, shows that the voltage proles are those expected for the lithium alloying process in silicon, xLi + Si / LixSi and, importantly, that the initial irreversible capacity is low. The value of the delivered specic capacity is of the order of 800 mAhg1. Considering that the amount of silicon in the composite is expected to be 30% and that the contribution of the graphite to the overall capacity may be estimated as 200 mAhg1, one may assume that for this particular composite electrode, the Li alloying process is not proceeding to completion (i.e., up to x 4.4). The capacity delivery upon cycling and the coulombic efciency values, however, are very stable and high, this conrming that the microstructure of this nano-Sigraphite composite is effective in buffering the volume expansion contraction upon the electrochemical cell. There are also indications that the amount of alloyed lithium, and thus the value of the capacity, can be enhanced by optimizing the morphology and the composition of the composite particles. The results reported for both tin and silicon conrm that moving to composite conguration is the right way to bring the related lithium alloy electrodes to commercial stage, and that the search for high capacity lithium metal alloy anodes may be considered successfully completed. In fact, their use is now seriously considered by battery manufactures. An example is provided by the SnCCo ternary composite that is presently exploited by a Japanese manufacturer to produce a battery that goes under the commercial name of Nexelion.22

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Fig. 5 Scheme and electrochemical process of a lithiumsulfur cell. Courtesy of Prof. K. Kim, Gyeongsang National University, South Korea.

4. The Holy Grail of batteries

One has to consider, however, that anodes are only part of a battery system, and that quantum jumps in overall energy density require also upgrading at the cathode side. So far, Li-ion battery chemistry has been based on intercalation-type electrodes that may accept a maximum of one lithium ion equivalent per mole of the host compound. This necessarily limits the specic capacity and thus to enhance energy density, new approaches
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must be undertaken. One is to pass from intercalation to conversion chemistry, namely to electrochemical processes that can ensure the exchange of much more lithium and thus, to offer orders of magnitude higher specic capacities. Along this line, a very promising system is the one provided by the lithiumsulfur, LiS cell, characterized by an electrochemical process involving a two-electron reaction: 2Li + S /Li2S to which a specic capacity of 1675 mAhg1(S) and an open circuit voltage of 2.23 V are associated, this leading to a theoretical energy density of 3730 Whkg1, i.e. almost one order of magnitude higher than that of conventional, intercalation chemistrybased Li-ion batteries. The structure of the lithium/sulfur battery and its related electrochemical process are schematized in Fig. 5. The concept of this battery is not new. However so far, the effective development of this high energy system has been prevented by a series of issues. A major one is associated with the high solubility of the cell reaction products in common lithium
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ion organic carbonate electrolytes. As schematically shown in Fig. 5, the electrochemical discharge process of the Li/S cell proceeds through the sequential formation of polysulphides LixSy which easily dissolve in the liquid carbonate electrolyte solutions and eventually diffuse to the lithium anode with severe corrosion effects.23,24 All of these events result in loss of active materials, low utilization of the sulphur cathode, low overall coulombic efciency and, ultimately, in severe capacity decay upon cycling. Another basic issue is the low electronic conductivity of S, Li2S and the intermediate Li-S products, which severely affects the rate capability of the battery. A nal problem, often overlooked, is the use of lithium metal as the preferred anode, which is known to cause serious safety risks due to uneven deposition upon charge, which may result in the shortage of the cell, with associated thermal runaway and, eventually, res or explosions. These hurdles have for some time cooled down the interest in lithium/sulfur battery. However, the attention towards this system rose again in the last years due to a series of important technological breakthroughs. Optimization in the fabrication of the cathode, passing from simple sulfurcarbon mixtures to sulfurcarbon composites, proved to be a successful approach for improving the conductivity of the electrode, as well as for controlling the solubility of the discharge products.2426 Another step forward in this technology was obtained by changing the cathode from the common sulfurcarbon composite to a lithium suldecarbon composite.27 In this way the cathode becomes the lithium ion source allowing to replace the reactive lithium metal with any other, more reliable lithiumaccepting material thus obtaining a metal-free, lithium-ion sulfur battery. This concept was rst demonstrated by using a tincarbon anode28,29 and was further conrmed with a siliconcarbon anode.30 These results consistently contributed to improve the technology of the lithium/sulfur battery; however, some residual issues still prevent the full practical exploitation of this high energy battery system. Most of the recent work relies on conventional liquid organic carbonate solution as the preferred electrolyte: although the sulfur and/or lithium sulde are shielded into a carbon matrix, either mesoporous25 or spherical,31 this in principle preventing the direct contact with the electrolyte, it is not yet fully established whether the issue of the solubility of the polysuldes has been successfully addressed. Possible steps forward may be achieved by moving from conventional liquid electrolytes to gel-type electrolyte membranes of suitable composition. A valid example is provided by a membrane formed by trapping a lithium conducting organic solution, added by a dispersed ceramic ller, in a poly(ethylene oxide)-lithium triuoromethanesulfonate, PEO-LiCF3SO3 matrix.28,29 One may simply describe this composite electrolyte as a membrane consisting in liquid zones contained within a polymer envelope. It is assumed that the polymer shell acts as a physical barrier to prevent contact of the polysulphide cathode products with the internal liquid solutions. Experimental results have in fact conrmed the validity of this approach.28,29 Even a more effective action to block the dissolution of the reaction products is expected to be provided by the use of totally solvent-free, solid-state, lithium conducting membranes, such as those formed by poly(ethylene oxide), PEO-lithium salt
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complexes.32 These membranes have been effectively tested as separators in lithiumsulfur cells by Jeong et al.33 and more recently in our laboratory.34 The results are quite encouraging, demonstrating that full capacity can be obtained by solid-state, PEO-based polymer Li/S-C batteries.34 An apparent issue is that these batteries have to operate around 7090  C. i.e. in the temperature range where the conductivity of the solid-state membranes reaches useful values.32 However, this cannot in effect be a dramatic penalty if the battery is used for applications where a moderately high temperature operation can be tolerated, such as in the electric vehicle area. Oxygen is in principle a cathode material even more exciting than sulfur. Its use may lead to the development of lithium-air batteries having a theoretical energy density reported as high as that provided by gasoline, although this assessment is somewhat questionable. It is this astonishing energy value, largely greater than that of any known battery, that has triggered worldwide frenzied interest in the lithium-air battery. There have been papers and press reports enthusiastically announcing that this battery is the power source of the future, i.e. the only device that may ensure the establishment of the electric vehicle market, dening it as the holy grail of batteries. Accordingly, research in lithium-air is heavily funded in various countries and a large number of academic and industrial laboratories are engaged in the lithium-air battery race. However, so far no real convincing evidence of the effective practical relevance has been reported. Severe issues, ranging from the reactivity of the lithium anode to the poor reversibility and efciency of the oxygen electrode, have so far limited the performance of lithium-air battery prototypes to few charge discharge cycles and to low rate capability. There are mainly two approaches, basically varying by the type of electrolyte used, that are presently exploited for the development of lithium-air batteries. One approach sees the use of an aqueous electrolyte in combination with a lithium metal electrode protected by a water-repulsive Li+ conductive glassceramic of the Nasicon type3537 or by an anion exchange membrane,38 see Fig. 6a. Here the overall electrochemical process is: O2 + 4Li + 2H2O / 4LiOH to which an estimated energy density of the order of 5000 Whkg1 is associated. This lithiumair aqueous battery operates preferentially in the primary mode. The remaining issues to be solved before achieving full practical exploitation are in the mechanical instability of the protecting lm, in its high interfacial resistance and in the solubility of the reaction products. The second approach considers the use of non-aqueous electrolytes.39 The battery represented in Fig. 6b by the classic scheme drawn by Bruce and co-workers,40 comprises a lithium metal anode, a separator embedded of the non-aqueous electrolyte, the carbon-supported air electrode (with or without catalyst) and a gas diffusion layer. This is the most appealing and studied version since its basic process 4Li + O2 / 2Li2O is the one that provides the highest theoretical energy density. Although the practical value is obviously affected by the weight of the ancillary battery components, e.g., air compressor and owing control, the energy expectations for the non-aqueous electrolyte lithium-air battery remain substantial. Unfortunately, the implementation of this non-aqueous system is compromised by a number of issues that exceed those previously discussed for
This journal is The Royal Society of Chemistry 2011

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Fig. 6 Lithium-air battery. (a) Aqueous electrolyte, protected anode design (courtesy of Dr Mark Salomon, Max Power Inc, USA); (b) non-aqueous electrolyte, unprotected lithium design (courtesy of Prof. Bruce, St. Andrews University, UK); (c) non-aqueous electrolyte, protected cathode design (courtesy of Dr Mark Salomon, Max Power Inc, USA). Taken from ref. 36 and 40 respectively, with permission from Elsevier (# 2647501083527) and Wiley Wiley-VCH STM Copyright.

the aqueous case. A major one is sensitivity to moisture: even traces of water must be avoided since their contact with the lithium metal electrode can seriously affect the reliability, safety and the cycle life of the battery. In open systems this requires the addition of an air scrubbing apparatus. As an alternative, cathode-protected designs exploiting a water-blocking membrane, can be used, see Fig. 6c. Obviously, these modications may affect the performance of the battery in terms of cost and energy density (weight of the additional ancillary parts), as well as of rate capability (large iR drop due to the limited ionic conductivity of the protective membrane). It is to be recalled here that high rate capability is a key requirement for batteries designed for electric vehicle applications. Another issue is the instability of non-aqueous electrolytes with respect with the electrochemical reaction species. In early studies,
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typical lithium-ion organic carbonate solutions were used. It is now ascertained that these electrolyte solvents are rapidly decomposed by the reaction products41,42 thus making the discharge dominated by electrolyte decomposition rather than the expected Li2O2 formation. Therefore, alternative, more stable electrolyte systems must be employed. Possible candidates are di-methoxy ethane DME-based or ionic-liquid-based solutions, although their use may be affected by overpressure (in the DME case) or by cost (in the IL case). A more promising choice is offered by polymer electrolytes, especially those based on poly(ethylene oxide)-lithium salt, e.g., PEO-LiCF3SO3 complexes.43 The well documented resistance of the PEO ether linkage combined with the stability towards nucleophiles of the LiCF3SO3 salt, is expected to provide a medium particularly suitable for lithium/air battery studies, as in fact experimentally demonstrated.37,43
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Finally, there are still thermodynamic and kinetics aspects that need to be claried. In addition, there is some confusion in the values of the specic capacity and of the related gravimetric energy density, that can be obtained by the system.39 Considering the quoted electrochemical process occurring in the lithium-air cell, i.e. 4Li + O2 / 2Li2O and properly taking into account both O2 and 4Li as the active materials, one obtains a specic capacity of 1790 mAhg1 and, assuming a potential of 2.91 V,39 an energy density of 5200 Whkg1. In some cases, however, the two parameters are reported as related to lithium only, excluding O2, thus leading to impressive, but questionable, 3682 mAhg1 and 11, 420 Whkg1 values. Probably, the most realistic approach is that assuming only O2 as the active material since this is in fact the specie that contributes to the electrochemical process; in this case the theoretical values of capacity and energy density are 3350 mAhg1 and 9,715 Whkg1, respectively. However, this choice poses some practical problems since temperature, volume and oxygen pressure are needed to estimate the number of moles, and thus the weight of the reacting oxygen, in any specic volume. Considering these difculties, the most commonly adopted method to estimate capacity is that of referring it to the electrode mass, either carbon, catalyst or both. However, also the values so obtained are not totally valid since, depending on the electrode surface and on the oxygen ux, they are not easily reproducible from one laboratory to another. Finally, results are also quoted for cells using Li2O as the working electrode. In this case the electrochemical process evolves according to the scheme: Li2O /1/2O2 + 2Li and the related specic capacity and energy density values, unambiguously referring to the Li2O weight, are 1787 mAhg1 and 5182 Whkg1, respectively.44,45 Another point of uncertainty has for some time been on the mechanism of the oxygen reduction process. Recent results4345 have claried that this process evolves through a series of steps, including the formation (via an intermediate O2 radical anion specie) of lithium superoxide LiO2 that subsequently transforms into lithium peroxide Li2O2 and eventually, to lithium oxide Li2O. The radical anion is a very strong base with high deprotonation activity that explains why conventional carbonate esters

cannot be used as electrolytes in lithium-air cells. Note also that Li2O2 and Li2O are electrically insulating products that, besides mechanically clogging the electrode owing to insolubility, impair the diffusion of oxygen and of electrolyte, thus originating an extra practical difculty. Due to all the above described unsolved issues, the state-ofthe-art lithiumoxygen (and not yet lithium-air!) batteries are far from being of real practical interest. A study reported in a recent paper46 shows that, on the basis of the presently achieved performance level of these batteries, to obtain the full automotive power of 100 kW required for EVs, a cell area of several thousand of square meters would be needed, an obviously unacceptable value. Considerable improvements are needed; in particular, charge and discharge rates have to be raised at the 10 mAcm2 level, namely an order of magnitude higher than the presently available one.46 An obvious way to increase the electrode kinetics is that of exploiting the aid of a catalyst for promoting the oxygen reduction process. Many materials have been proposed, including a series of manganese, iron, nickel, cobalt and copper oxides.42,45 However, the activity of the catalysts may be compromised by various negative effects intrinsic to the battery medium, such as precipitation on the catalyst surface of Li2O2 formed during discharge and/or dissolution of the nanometric catalyst particle into the electrolyte. In addition, in view of the complex reaction mechanism, see above, it cannot be given for granted that both the reduction and the re-oxidation process can be inuenced by the same catalyst compound. Indeed, recent work by Gasteiger and co-workers has shown that 75% efciency of the battery processes can only be achieved with the use of bifunctional Pt/Au catalyst, see Fig. 7.45 Unfortunately, the cost barrier may exclude practical use of this material, and more realistic options have to be identied. Lithium-air is undoubtedly a most fascinating energy storage system and this accounts for the large attention and considerable funding presently devoted to its investigation and development. The route, however, towards making the lithium-air battery feasible for vehicle applications is still long, especially considering that so far most of the studies have been limited to oxygen fuelled systems, while cost effectiveness and practical feasibility, obviously require the use of air cathodes.

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5. Are we running out of lithium?

We may conclude this brief overview on the lithium systems by tackling the question of the availability of the metal in view of the amount needed for ensuring large road diffusion of electric transportation. Doubts have been raised on whether the lithium in the earths crust can be sufcient to satisfy this request. The doubts are groundless since lithium is indeed greatly abundant. Lithium carbonate reserves in the salt mines in South America comprise several billion cubic meters of brine. Recently a new deposit, discovered in Afghanistan, has been estimated to have a value of thousand billions of dollars to the point that Afghanistan has been identied as one of the possible main lithium supplying countries, although the present situation makes it difcult to foresee an easy operation of these reserves. Resources of lithium are also available in sea water although in a lower content than sodium. Altogether, the availability of lithium
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Fig. 7 Li-O2 cell discharge/charge proles of carbon (black, 85mA g1carbon) and PtAu/C (red, 100 mA g1carbon) in the third cycle at 0.04 mA cm2electrode. Adapted with permission from ref. 45. Copyright 2011 American Chemical Society.

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amounts to several hundred thousand of megatonnes, and thus its content appears to be more than sufcient to meet the demand, even in the improbable case of total conversion of the gasoline-powered cars into hybrids or electric cars.

Acknowledgements
This research was supported in part by the Italian Institute of Technology in the framework of the SEED Project REALIST (Rechargeable, advanced, nano-structured lithium batteries with high energy storage) and by the WCU (World Class University) program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (R31-2008-000-10092)

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