BRIEFING No.

32

TRANSPORT
Nanotech in next-generation electric car batteries: beyond Li-ion
Batteries specifically fabricated for future Electric Vehicles (EVs) have to satisfy a demanding set of automotive and market requirements, the most important being high energy capacity, long and stable life with deep cycles, fast charging and safety. Li-ion batteries, the most popular technology for EVs currently, are expected to reach their performance limits by 2020 (about 200 Wh/kg, giving a driving of 350km for a 200kg battery).1 New battery technologies will need to be developed that will drive EVs further and allow them to be used in a similar way to current internal combustion engine (ICE) vehicles. Such battery technologies currently in the stage of research are Li-air, Li-S, zinc-air and magnesium batteries. These technologies however present some fundamental problems in their functionality. What role can nanotechnology play in overcoming them in order to create the EV batteries of the future?

ObservatoryNANO Briefing March 2012

How can nano help/add value?

Recently there has been much interest in the application of nanotechnology structures (<100nm) applied to Li-ion battery design, e.g. A123 Systems has developed a lithium iron phosphate battery and Altair Nanotechnologies, which has developed lithium titanate as an electrode material.2 Producing smaller particles, coating the particles in carbon, mixing the cathode material with conducting fibres, nanostructuring for short diffusion distances or doping with various additives are some of the methods of improving the attributes of battery electrodes and electrolytes.3,4 The use of nanotechnology has some advantages and disadvantages.5 Advantages It enables electrode reactions to occur that cannot take place for materials composed of micrometre-sized particles; for example, reversible lithium intercalation into mesoporous b-MnO2 without destruction of the rutile structure. The reduced dimensions increase significantly the rate of lithium insertion/removal, because of the short distances for lithium-ion transport within the particles. The characteristic time constant for diffusion is given by t = L2/D, where L is the diffusion length and D the diffusion constant. The time t for intercalation decreases with the square of the particle size on replacing micrometre with nanometre particles. Electron transport within the particles is also enhanced by nanometre-sized particles, as described for lithium ions. A high surface area permits a high contact area with the electrolyte and hence a high lithium-ion flux across the interface.

For very small particles, the chemical potentials for lithium ions and electrons may be modified, resulting in a change of electrode potential (thermodynamics of the reaction). The range of composition over which solid solutions exist is often more extensive for nanoparticles, and the strain associated with intercalation is often better accommodated. Disadvantages Nanoparticles may be more difficult to synthesize and their dimensions may be difficult to control. High electrolyte/electrode surface area may lead to more significant side reactions with the electrolyte, and greater difficulty in maintaining inter-particle contact. The density of a nanopowder is generally less than the same material formed from micrometre-sized particles. The volume of the electrode increases for the same mass of material thus reducing the volumetric energy density. Similar nano-traits can perhaps be sought for in new battery technologies beyond Li-ion.

Li-S
Li-S has great potential especially regarding its high energy density (about 2600 Wh/kg7) with a practical energy density reaching 250-500 Wh/kg. The theoretical capacity of lithium-sulphur batteries is higher than that of lithium-ion batteries because of the way the ions are assimilated at the electrodes. E.g., at the sulphur electrode, each sulphur atom can host two lithium ions. Typically, in lithium-ion batteries, for every host atom, only 0.5 to 0.7 lithium ions can be accommodated

1
Figure 1: Schematic representations of Li-ion, non-aqueous and aqueous LiO2 and LiS cells.6

TRANSPORT: Next Gen Batteries for Electric Vehicles

From the manufacturing side, Li-S is similar to Li-ion technologies, which makes the makeover of the vehicle as well as the makeover of the battery production process easier and cheaper. Li-air batteries on the contrary would require a much greater investment for adjusting vehicles and production plants, as they resemble more fuel cells. Some of the main challenges that Li-S batteries face are: Relatively low practical specific energy at the cell level (250-500 Wh/kg vs. the cathodes theoretical 2600 Wh/kg). The energy density stated by the different researchers is 2 to 5 times higher than current developed Li-ion EV batteries. Making materials that take advantage of this higher theoretical capacity has been a challenge. One big issue has been that sulphur is an insulating material, making it difficult for electrons and ions to move in and out. So while each sulphur atom may in theory be able to host two lithium ions, in fact often only those atoms of sulphur near the surface of the material accept lithium ions. Measurements of the exact energy density in complete battery systems should be made to have an idea about the real market potential of the technology. If the gains in energy density are not distinctively high, the question arises whether the technology is worth the investment. Safety concerns, related to the Li-metal reactivity. During use, the lithium electrode can grow branchlike structures (dendrites) that can cause a short circuit. If the battery heats up, the metal can melt. If the molten lithium leaks out of the cell and comes into contact with water, it can start a fire.8 This major issue also affects the usable lifetime of the battery. Research effort is focusing on decoupling the Li-metal from the electrolyte, to make a so-called protected Lithium anode. Other research lines focus on replacing the Li-metal with materials that do not grow dendrites. Cyclability issues: As the sulphur binds to lithium ions during charging, eventually forming dilithium sulphide, it forms a number of intermediate products called polysulphides. The polysulphides are easily dissolved in the electrolyte and can react at the anode. Therefore there is a continuous loss of active material (sulphur) resulting in significant decrease in capacity during cycling (0.1-0.4 % per cycle) and very limited cycle life (50-100 cycles). For application in electric vehicles the target of 1000-5000 cycles has to be achieved. Other issues include that the electrolyte is not thermodynamically stable at the low Li-potentials and high self-discharge rates (8-15% per month)9 NMR (nuclear magnetic resonance) is also being used to understand the in-situ degradation of the electrolyte (Prof. Clare Grey, University of Cambridge), while other groups have been using TEM (transmission electron microscopy). Dr. Katerina Aifantis (Aristotle University of Thessaloniki), who focuses on the mechanical integrity of anodes, indicates that "a major issue that remains open is the examination of the microstructural changes that sulphur undergoes during Li-insertion. No transmission electron microscopy investigations have been performed yet on cycled sulphur cathodes to indicate if fracture occurs, as in Si and Sn based anodes." It is worth noting that damage in anodic materials, such as Si and Sn, is severe since the volume expansion can reach up to 300%, on the formulation of Li-rich phases.11 Different applications of nanotechnology within Li-S batteries: New Nanostructured Li2S/Silicon Rechargeable Battery with High Specific Energy12 (Li2S/mesoporous carbon nanocomposite cathode and a silicon nanowire anode) Hollow carbon nanofibre-encapsulated sulphur cathodes for high specific capacity rechargeable lithium batteries developed by the nanotechnology group of Prof. Yi Cui at Stanford University.13 Improving the Performance of LithiumSulphur Batteries by Conductive Polymer Coating14 Graphene-wrapped sulphur particles as a rechargeable lithium-sulphur battery cathode material with high capacity and cycling stability.15 Graphene oxide-sulphur (GO-S) nanocomposite cathodes16 Impregnating sulphur into disordered carbon nanotubes (DCNTs) as a cathode material for Li-S batteries.17 ZrO2 nanofiller in a polymer electrolyte for a tinsulphur battery18 Siliconcarbon nanocomposite anode for a metalfree Silicon-Sulphur battery19

ObservatoryNANO Briefing March 2012

Figure 3: Sketch of novel lithium metal-free battery30

2
Figure 2: Status of Lithium Sulphur Technology10

To overcome these challenges, new molecules and additives need to be developed for the electrolyte, sulphur cathode, protected lithium anode. The R&D for these molecules is mainly carried out in the micro-scale rather than in the nano-scale. Despite the scientific research work carried out in the nanoscale, industrial experts emphasize that today nanomaterials do not play any role in overcoming the major problems (cyclability, lifetime, etc.) that Lithium-Sulphur technology faces.

TRANSPORT: Next Gen Batteries for Electric Vehicles

Li-air
Over the recent years a lot of hype has accumulated around Li-air batteries, mainly due to their very high specific energy density (theoretical more than 10 000 Wh/kg). In practice their estimated specific energy is much lower, about 1/10th of that if not less. A recent reported application reached a specific energy of 362 Wh/kg, just twice higher than current Li-ion batteries.20 Li-air has many challenges, both in the electrodes and in the electrolyte. Most of these challenges could be addressed with the aid of nanotechnology. Anode - Inherent problems of lithium metal: Dendrite formation/ efficiency, require stable SEI, safety issues. Alternative anodes considered such as LixSi, LixSn. Cathode - needs to effectively block CO2 and H2O while allowing enough O2 to pass through, perhaps with a nanoporous membrane. Voltage difference between charging and discharging must be reduced. Capacity fading after only a few cycles. Electrolyte - Stability window, Conductivity, Volatility, O2 solubility and diffusivity. As IBM reports from its Battery 500 project21, commonly used electrolytes for conventional lithium ion batteries are being destroyed in a lithium air battery and do not work. But several other electrolytes do show clear evidence of supporting charging and recharging, indicating that the choice of electrolytes for these batteries is very critical.22 The decomposition and consumption of the electrolytes was observed in many publications.23,24 Polymer25 or silane26 electrolytes seem to give interesting results. Electrokinetics - The reaction between oxygen and lithium is intrinsically slow, far too sluggish to give sufficient acceleration for a car. The efficiency of metalair batteries is significantly limited by the activation of oxygen reduction and evolution reactions. Increasing the surface area of the individual electrode particles can increase the rate at which the battery can charge and discharge.27 Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Electrochemical Strain Microscopy (ESM)28 could help in this direction. Different applications of nanotechnology within Li-O2 batteries: PlatinumGold Nanoparticles: A Highly Active Bifunctional Electrocatalyst for Rechargeable LithiumAir Batteries29 Hierarchically Porous Graphene as a LithiumAir Battery Electrode30 -MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries31 Palladium nanocatalysts and Palladium oxide nanocatalysts on the air cathode32 Nanostructured Diamond Like Carbon Thin Film Electrodes for Lithium Air Batteries33

ObservatoryNANO Briefing March 2012

Nitrogen-doped Graphene Nanosheets as Cathode Materials with Excellent Electrocatalytic Activity for High Capacity Lithium-oxygen Batteries34 Nanostructured electrodes for lithium-ion and lithium-air batteries: the latest developments, challenges, and perspectives35 Carbon nanotube/Co3O4 composite for air electrode of lithium-air battery36

Figure 4: -MnO2 Nanowires39

Polyvalent Multivalent batteries: the case of the Magnesium anode

Batteries utilizing polyvalent cations such as Ca2+, Mg2+, and Y3+ in place of univalent lithium are being considered to increase the number of electrons transferred at the cell voltage per cation. Since lithium accounts for a small portion of the active material mass in lithium ion batteries, substituting a heavier cation with over twice the charge capacity could increase energy storage disproportionally to the mass increase, allowing higher specific energy. However, diffusion of polyvalent cations through the cathode material is much lower than for lithium and suitable electrolytes and anodes have not been developed for these cations.37 Low cost, non-dendritic magnesium metal is an ideal anode for a post lithium ion battery. Mg anode has the advantage that it is not plagued by dendritic growth, is safer than Li when exposed to air, is more abundant in the earth crust (24 times cheaper than Li) and has double the volumetric capacity of Li metal. Key challenges in developing a Mg battery are to find new solvents which mitigate polysulfide dissolution, optimize the sulphur cathode morphology and develop a noncorrosive electrolyte with wide electrochemical window needed for high voltage cathodes (> 3.5V)38 Currently, the development of magnesium electrolytes governs the rate of progress in this field, because electrolyte properties determine the class of cathodes utilized. One conversion cathode of particular interest that has been identified is electrophilic sulphur which can be married with magnesium metal anodes by utilizing nonnucleophilic electrolytes obtained by simple crystallization of in situ generated magnesium organohaloaluminates. Effectively, non-nucleophilic electrolytes open the door to research on magnesium/sulphur batteries.39 Prof. Doron Aurbach from Israel has been making progress in developing the world's first rechargeable magnesium battery. In 2000, Aurbach's group is reported to have solved both these problems.40 The team used electrolyte solutions based on 'magnesium organohaloaluminate' salts and 'MgxMo 3S4' cathodes to build a prototype magnesium battery about the size of a computer monitor. Companies following down that approach include Toyota and MIT spin-off, Pellion Technologies.41

TRANSPORT: Next Gen Batteries for Electric Vehicles

Zinc-air rechargeable batteries
Zinc-air batteries, which use zinc metal as the anode and an alkaline paste as the electrolyte, are simple, inexpensive, nontoxic, and long lasting. But engineers have been unable to resolve how to recharge them. The US spin-off company Fluidic Energy in 2007 is quoted to have solved the problem by using a porous electrode and a liquid solution of zinc ions and additives as the electrolyte.42 However, to date no practical cell of this type has been made as a prototype for manufacturing purposes. In the EU, research collaboration in zinc-air batteries takes place under FP7 project Polyzion (http:// www.polyzion.eu/), expected to be completed by September 2012. The project aims to develop a reversible and stable Zn/Zn2+ redox couple for secondary zinc cells, with charge-discharge efficiency and cyclability greater than 90% and 1000 cycles, using an Ionic liquid electrolyte, zinc nanocrystalites and a conducting polymer electrode. It is worth noting, though, that one of the main barriers that have prohibited the industrial uptake of ionic liquids is their manufacturing process, which is still at lab scale and cost. Zinc-air batteries are not considered as suitable for use in future full-electric vehicles, but rather for back-up power static applications, according to industrial players such as BASF. efforts go into chemistries that do not require rareearth materials for example. Lithium production is already being ramped up, while sulphur, for example, is a very attractive material as it is a by-product of the oil refining process.

Technology Readiness Levels

ObservatoryNANO Briefing March 2012

Figure 5: TRL funnel for (automotive) battery technologies

Impact
Economic/Industry
Demand for full-electric vehicle batteries will reach around 70 million kWh by 2020.43 With a targeted cost of 200/kWh, that calculates to an estimated market of about 14 billion. To reach that demand though, EVs must reach a usable range that suits the daily needs of modern drivers. BASF thinks lithium-sulphur batteries could achieve 500Wh/kg, making a 500km range EV a possibility by 2020-2030.44 Lithium-air technology and other technologies are also being developed as part of BASF's advanced R&D, however Li-air is not expected to reach market maturity before 2030-40 perhaps. According to Thierry Koskas from Renault, 200/kWh x 10 years of life (1000-2000 cycles) is a good tipping point for bringing use prices of EVs lower than that of ICEs (around 0.1 /km). Reducing battery cost and improving durability are the main factors to improve in order to reach that goal. Ford on the other hand focuses on reducing size and weight of the battery for the same capacity. Ted Miller of Ford stated that they are betting on breakthroughs from new chemistries such as zinc-air or lithium-air, especially as the OEM moves towards its final goal of 55kg and 60 litres, a huge reduction since its firstgeneration Li-ion battery pack on the electric Focus that weighs over 225kg and has a volume of 125 litres. The future will require ultra high density electrodes, whether its lithium-sulphur or a metal-air battery, said Miller.45 Future supply of raw materials for the scale up of the EV battery production is a topic of consideration as well among industries. When developing new technologies,

EHS Impacts
Properties of materials at the nanoscale are different to those in bulk form. For example, specific surface area increases, potential to translocate is higher, and solubility is altered. As a result, some materials at the nanoscale may have potential to present a risk to health and the environment. Currently, there is a lack of knowledge on both the hazard and exposure of such materials and as a result, current data is insufficient to enable adequate risk assessment. Therefore, the importance of safety by design and responsible development from research to market application in order to reduce potential risk is paramount. For batteries, the potential for exposure to workers exists during the manufacturing process, however the use of appropriate exposure control measures is likely to provide sufficient protection against potential harm. Exposures (to workers and the environment) are also possible during disposal at end of life, depending on the process chosen. No exposure is likely however during use (service life) and so no risks to consumers are foreseen. Relevant industries in the chemistry sector report though that nanotechnology had always played a role, even limited, in battery chemistry. Protective measures for the workers and general safety procedures have been followed continuously and are not something new for them.

Societal Impact on European Citizen

From a societal perspective, improving batteries for electric vehicles is one of several potential contributions to more sustainable mobility. However, safety, life cycle aspects and the socio-economic impact on developing countries depending on export of incorporated or

TRANSPORT: Next Gen Batteries for Electric Vehicles

replaced raw materials should be taken into account. Furthermore, even if the electric car with nano-enabled battery is more sustainable than other cars, this positive effect could be cancelled out by rebound effects, for example if consumers use new cars more because they think they are less polluting. Sustainable vehicles have to be combined with a more sustainable production of energy. Considering the above points, one can assume that Europe has equal chances to become the leading region for future automotive batteries in the future as any other region. Providing financial support to research and industrial activities, as well as tools and stimuli for the support of innovative start-ups may be key to being successful.

ObservatoryNANO Briefing March 2012

Summary
Li-air, Li-S, Mg-S are some of the battery technologies with high energy density potential that are being developed by researchers in Europe and the world. Such technologies could be used in future massmarketed EVs (2020 and later) giving them a range of 350 km or even more. However these technologies still face serious technical issues, including their cyclability, lifetime and safety. Intense R&D needs to be carried out both in basic research and industrial scale-up. Producing smaller particles, coating the particles in carbon, mixing the cathode material with conducting fibres, nanostructuring for short diffusion distances or doping with various additives are some methods of improving the attributes of battery electrodes and electrolytes. From an industrial point of view, however, nanotechnology does not play a major role in the current phase of development of these battery technologies; it could play a role in the future though, in a similar way to Li-ion batteries nowadays. The race for becoming the leading world region in battery production seems to be on, but still quite unpredictable.

EU Competitive Position
Europe is the base of several major industrial players in the automotive battery field including Axeon, Saft/Renault, Cegasa, SB Limotive, and li-Tec (Evonik-Daimler JV). In academia, EU research on EV batteries is strongly led by the universities of St. Andrews, Picardie Jules Verne, Sapienza, Munich, Munster and Cambridge, as well as by professors affiliated with the European ALISTORE-ERI network (http://www.alistore.eu/). Important researchindustry cooperation in Europe include the HE Lion / LIB 2015 BMBF funded consortium in Germany, the Polyzion FP7 research project, the BELLA joint laboratory by KIT and BASF, as well as a cooperation between St. Andrews and Toyota.22 Future leadership on Li-S is likely foreseen in such high -tech knowledge intensive regions like EU, USA and Japan, rather than in low-labour costs regions such as China, says BASF. The research generated in the USA, China, Korea, Japan and Canada seems to be competing strongly with Europe, with many publications appearing in scientific journals and science databases. The US is raising a lot of hype mostly around Li-air technology through numerous publications and media attention, even though one cannot say Li-air is the safest bet yet. The DOEs Advanced Research Project Agency-Energy Initiative (ARPA-E) announced $106 million in energy research project grants in 2010. Included in the DOE funding was nearly $35 million for the Batteries for Electrical Energy Storage in Transportation (BEEST) program that seeks to develop a new generation of ultra-high energy density, low-cost battery technologies for long range plug-in hybrid and all-electric vehicles.46 One of the EUCAR and CLEPA suggested R&D objectives for 2009 for the EU Green Car Initiative was Basic research on new open cell systems technology (post Lithium-ion battery cells) for highest energy density focussing on electrochemistry of battery cells and storage capacitors (packaging, crashworthiness, durability, reliability, adoption to different vehicle concepts) with an appropriate level of safety47 The impression is that battery research in the US is better funded than in the EU, as Dr. Scott Lilley from the University of St. Andrews commented, as well as perhaps more strategic, although Germany could be considered an exception. Industry experts believe that the race for the future of automotive batteries is still very much unpredictable. For reaching a successful high-energy battery for future EVs, a mixed portfolio of battery technologies may need to be researched. Its still unclear what is going to work, said John Muldoon, principal researcher for post Li-ion technologies at Toyota. Aluminium is a good candidate, as is magnesium and calcium, so too lithium-ion and perhaps lithium-sulphur. All of these players are important.48

Contact Information
Harilaos Vasiliadis Bax & Willems Consulting Venturing h.vasiliadis@bwcv.es

Suggested further reading

Nanostructured electrodes for Li-ion & Li-air batteries
http://dx.doi.org/10.1016/j.mser.2011.06.001 LiO2 and LiS batteries with high energy storage http:// dx.doi.org/10.1038/nmat3191 Lithium batteries: Status, prospects and future, http:// dx.doi.org/10.1016/j.jpowsour.2009.11.048 High Energy Density Lithium Batteries, http://eu.wiley.com/ WileyCDA/WileyTitle/productCd-3527324070.html A metal-free, lithium-ion, siliconsulphur battery http:// dx.doi.org/10.1016/j.jpowsour.2011.11.060 Nanomaterials for Rechargeable Lithium Batteries. http:// dx.doi.org/10.1002/anie.200702505 Electrolyte roadblocks to a magnesium rechargeable battery http://dx.doi.org/10.1039/C2EE03029B

TRANSPORT: Next Gen Batteries for Electric Vehicles

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Hassoun, J. and Scrosati, B. (2010), A High-Performance Polymer Tin Sulfur Lithium Ion Battery. Angew. Chem. Int. Ed., 49: 2371 2374. doi: 10.1002/anie.200907324 19. J. Hassoun, J. Kim, D.-J. Lee, H.-G. Jung, S.-M. Lee, Y.-K. Sun, B. Scrosati, A contribution to the progress of high energy batteries: A metal-free, lithium-ion, siliconsulfur battery, Journal of Power Sources, Volume 202, 15 March 2012, Pages 308-313, ISSN 03787753, 10.1016/j.jpowsour.2011.11.060. 20. J.-G. Zhang et al. "Ambient Operation of Li/Air Batteries", J. Power Sources 195, 4332 (2010). 21. http://www.ibm.com/smarterplanet/us/en/smart_grid/article/ battery500.html 22. Winfried Wilcke, Lithium/Air Battery Project (abstract), Automotive Battery Conference 2012 23. Freunberger, S. A., Chen, Y., Drewett, N. E., Hardwick, L. J., Bard, F. and Bruce, P. G. (2011), The LithiumOxygen Battery with EtherBased Electrolytes. Angewandte Chemie International Edition, 50: 86098613. 24. Stefan A. 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Muldoon, Multivalent Post Li-ion Batteries, presentation at EV Battery Technology 2012, London 39. J. Muldoon, et. al., Electrolyte roadblocks to a magnesium rechargeable battery, Energy Environ. Sci., 2012, 5, 5941-5950, DOI: 10.1039/C2EE03029B 40. Aurbach,D. et al., Prototype systems for rechargeable magnesium batteries, Nature 407, 724 727, 2000. 41. http://arpa-e.energy.gov/ProgramsProjects/BEEST/ LowCostRechargeableMagnesiumBatterieswithHig.aspx 42. Cody Friesen, Making cheaper, higher-energy batteries to store renewable energy, Technology Review, 2009 - http:// www.technologyreview.com/tr35/Profile.aspx?TRID=776 43. Powertrain 2020; Li-Ion batteries the next bubble ahead? , Roland Berger, 2010 44. http://ae-plus.com/news/basf-combines-all-elements-in-batteryrandd 45. Smaller EV batteries, Automotive Engineer, 3 April 2011 - http://ae -plus.com/news/smaller-ev-batteries 46. Scott Faris, Tech Journal, Advanced battery tech will drive auto industry, 26 August 2010 - http:// www.techjournalsouth.com/2010/08/advanced-battery-tech-willdrive-auto-industry/ 47. R&D Priorities for the Greening of Vehicles and Road Transport - A contribution by CLEPA and EUCAR to the European Green Car Initiative, May 2009 48. Essential elements, Automotive Engineer, 13 June 2011, http://aeplus.com/features/essential-elements/page:3

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