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176 B.L. Ellis, L.F. Nazar / Current Opinion in Solid State and Materials Science 16 (2012) 168–177 technology provide intriguing possibility with very high capacities as well as relatively low polarization. In terms of ambient-temperature cells that operate on the basis of intercalation chemistry, many positive electrode materials reported thus far have been analogues of various Li-battery mate- rials such as the layered oxides, NASICON compounds and olivines. Typically, the sodium and lithium compounds are not strictly iso- structural though, especially in the case of polyanion materials where the influence of the alkali size/charge ratio is significant in determining the thermodynamically most stable phase. Thus, dif- ferent electrochemical properties result and intriguing differences have emerged between the Li+ and Na+ cation systems. Similar observations are true for negative electrode materials: hard car- bons, but not the graphitic materials that are used in Li-ion cells, have been reported to be active Na-ion intercalation compounds at low potential. Much scope for porous carbon design lies in this area. Sodium metal dioxides based on vanadium and titanium have also been studied for their low voltage properties. Intriguingly, modelling studies have revealed that the activation energy for Na+-ion hopping is often lower than for Li+ (perhaps due to less polarization), especially for layered oxides. The generally lower voltage of Na compounds also provides considerable advantages for negative electrode development by increasing the overall volt- age and hence energy density. Of course, the potential of the so- dium-containing positive electrode would be similarly lowered, but here there is the opportunity to explore materials where the lithium analogues have too high a potential to support many con- ventional electrolytes. Based on electrochemical studies – not surprisingly – open and layered structures which are better able to accommodate the large Na+ ions have proven to hold the most promise of the intercalation compounds. In terms of phase stability, these structures also gen- erally have exhibit Na and Li versions of the same compound. How- ever, as illustrated by Na2FePO4F, the development of new structures and framework types based specifically on sodium (i.e., not variations on the lithium analogue) are more likely to be pivotal for advancement of the Na-ion battery field. For intercala- tion systems, this means overcoming the larger volume expan- sion/contraction afforded by the sodium cation with clever solid state structure design. Overall, though, it is clear that Na-ion bat- teries can vie with Li-ion batteries in several important respects, and there is furthermore much opportunity and promise in this area. Acknowledgments NSERC is acknowledged for financial assistance through the Dis- covery Grant Program and for generous support via a Canada Re- search Chair to LFN. We are especially grateful to General Motors and NSERC for funding through the Collaborative Research Program. References [1] Tarascon JM, Armand M. Issues and challenges facing rechargeable lithium batteries. Nature 2001;414:359. [2] Risacher F, Fritz B. Origin of salts and brine evolution of Bolivian and Chilean Salars. Aquat Geochem 2009;15:123. [3] Yaksic A, Tilton JE. Using the cumulative availability curve to assess the threat of mineral depletion: the case of lithium. Resour Policy 2009;34:185. [4] Fang Y, Yao Y, Kummer JT. Ion exchange properties of and rates of ionic diffusion beta alumina. J Inorg Nucl Chem 1967;29:2453. [5] J.T. 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