In the search for improved energy storage, rechargeable metal–oxygen batteries are very attractive owing to their reliance on molecular oxygen, which forms oxides on discharge that decompose reversibly on charge. Much focus has been directed at aprotic Li–O2 cells, but the aprotic Na–O2 system is of equal interest because of its better reversibility. We report here on the critical role and mechanism of phase-transfer catalysis in Na–O2 batteries. We find that it is solely responsible for the growth and dissolution of micrometre-sized cubic NaO2 crystals and for the reversible cell capacity. In the absence of phase-transfer catalysis, quasi-amorphous NaO2 films are formed and cells exhibit negligible capacity. Electrochemical investigations provide a measure of the transportation of superoxide from the carbon electrode to the electrolyte phase by the phase transfer catalyst. This leads to a new understanding of the mechanism of Na–O2 batteries that, significantly, extends to Li–O2 cells and explains their different behaviour.
Subscribe to Journal
Get full journal access for 1 year
only $13.33 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Abraham, K. M. & Jiang, Z. A polymer electrolyte-based rechargeable lithium/oxygen battery. J. Electrochem. Soc. 143, 1–5 (1996).
Kraytsberg, A. & Ein-Eli, Y. J. Review on Li–air batteries—opportunities, limitations, and perspective. J. Power Sources 196, 886–893 (2011).
Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J. M. Li–O2 and Li–S batteries with high energy storage. Nature Chem. 11, 19–29 (2012).
Black, R., Adams, B. & Nazar, L. F. Non-aqueous and hybrid Li–O2 batteries. Adv. Energy Mater. 2, 801–815 (2012).
McCloskey, B. D. et al. The twin problems of interfacial carbonate formation in non-aqueous Li–O2 batteries. J. Phys. Chem. Lett. 3, 997–1001 (2012).
Thotiyl, M. M. O., Freunberger, S. A., Peng, Z. & Bruce, P. G. The carbon electrode in nonaqueous Li–O2 cells. J. Am. Chem. Soc. 135, 494–500 (2013).
Sharon, D. et al. Oxidation of dimethyl sulfoxide solutions by electrochemical reduction of oxygen. J. Phys. Chem. Lett. 4, 3115–3119 (2013).
Kwabi, D. et al. Chemical instability of dimethyl sulfoxide in lithium–air batteries. J. Phys. Chem. Lett. 5, 2850–2856 (2014).
Walker, W. et al. A rechargeable Li–O2 battery using a lithium nitrate/N,N-dimethylacetamide electrolyte. J. Am. Chem. Soc. 135, 2076–2079 (2013).
Elia, G. A. et al. An advanced lithium–air battery exploiting an ionic liquid-based electrolyte. Nano Lett. 14, 6572–6577 (2014).
Meini, S., Piana, M., Nikolaos, T., Garsuch, A. & Gasteiger, H. A. The effect of water on the discharge capacity of a non-catalyzed carbon cathode for Li–O2 batteries. Electrochem. Solid-State Lett. 15, A45–A48 (2012).
Meini, S., Solchenbach, S., Piana, M. & Gasteiger, H. A. The role of electrolyte solvent stability and electrolyte impurities in the electrooxidation of Li2O2 in Li–O2 batteries. J. Electrochem. Soc. 161, A1306–A1314 (2014).
Schwenke, K. U., Metzger, M., Restle, T., Piana, M. & Gasteiger, H. A. The influence of water and protons on Li2O2 crystal growth in an aprotic Li–O2 cell. J. Electrochem Soc. 162, A573–A584 (2015).
Aetukuri, N. B. et al. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nature Chem. 7, 50–56 (2015).
Johnson, L. et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nature Chem. 6, 1091–1099 (2014).
Adams, B. D. et al. Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge. Energy Environ. Sci. 6, 1772–1778 (2013).
Horstmann, B., Gallant, B., Mitchel, R. R., Bessier, W. G. & Shao-Horn, Y. Rate-dependent morphology of Li2O2 growth in Li–O2 batteries. J. Phys. Chem. Lett. 4, 4217–4222 (2013).
Chen, Y. H., Freunberger, S. A., Peng, Z. Q., Fontaine, O. & Bruce, P. G. Charging a Li–O2 battery using a redox mediator. Nature Chem. 5, 489–494 (2013).
Lim, H. D. et al. Superior rechargeability and efficiency of lithium–oxygen batteries: hierarchical air electrode architecture combined with a soluble catalyst. Angew. Chem. Int. Ed. 53, 3926–3931 (2014).
Bergner, B. J., Schürmann, A., Peppler, K., Garsuch, A. & Janek, J. TEMPO: a mobile catalyst for rechargeable Li–O2 batteries. J. Am. Chem. Soc. 136, 15054–15064 (2014).
Bender, C. L., Hartmann, P., Vračar, M., Adelhelm, P. & Janek, J. On the thermodynamics, the role of the carbon cathode, and the cycle life of the sodium superoxide (NaO2) battery. Adv. Energy Mater. 4, 1301863 (2014).
Peled, E., Golodnitsky, D., Mazor, H., Goor, M. & Avshalomov, S. Parameter analysis of a practical lithium– and sodium–air electrical vehicle battery. J. Power Sources 196, 6835–6840 (2011).
Hartmann, P. et al. Rechargeable room-temperature sodium superoxide (NaO2) battery. Nature Mater. 12, 228–232 (2013).
Kim, J., Lim, H. D., Gwon, H. & Kang, K. Sodium–oxygen batteries with alkyl-carbonate and ether based electrolytes. Phys. Chem. Chem. Phys. 15, 3623–3629 (2013).
Ren, X. & Yu, Y. A low-overpotential potassium–oxygen battery based on potassium superoxide. J. Am. Chem. Soc. 135, 2923–2926 (2013).
Laoire, C. O., Mukerjee, S. & Abraham, K. M. Elucidating the mechanism of oxygen reduction for lithium–air battery applications. J. Phys. Chem. C 113, 20127–20134 (2009).
Peng, Z. Q. et al. Oxygen reactions in a non-aqueous Li+ electrolyte. Angew. Chem. Int. Ed. 50, 6351–6355 (2011).
Xia, C. et al. Evolution of Li2O2 growth and its effect on kinetics of Li–O2 batteries. ACS Appl. Mater. Interfaces 6, 12083–12092 (2014).
Yang, J. et al. Evidence for lithium superoxide-like species in the discharge product of a Li–O2 battery. Phys. Chem. Chem. Phys. 15, 3764–3771 (2013).
Kang, S. Y., Mo, Y., Ong, S. P. & Ceder, G. Nanoscale stabilization of sodium oxides: implications for Na–O2 batteries. Nano Lett. 14, 1016–1020 (2014).
Sun, Q., Yang, Y. & Fu, Z. W. Electrochemical properties of room-temperature sodium–air batteries with non-aqueous electrolyte. Electrochem. Commun. 16, 22–25 (2012).
Liu, W., Sun, Q., Yang, Y., Xie, J. Y. & Fu, Z. W. An enhanced electrochemical performance of a sodium–air battery with graphene nanosheets as air electrode catalysts. Chem. Commun. 49, 1951–1953 (2013).
Jian, Z. et al. High capacity Na–O2 batteries with carbon nanotube paper as binder-free air cathode. J. Power Sources 251, 466–469 (2014).
Li, Y. et al. Superior catalytic activity of nitrogen-doped graphene cathodes for high energy capacity sodium–air batteries. Chem. Commun. 49, 11731–11733 (2013).
Yadegari, H. et al. On rechargeability and reaction kinetics of sodium–air batteries. Energy Environ. Sci. 7, 3747–3757 (2014).
Hartmann, P. et al. A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery. Phys. Chem. Chem. Phys. 15, 11661–11672 (2013).
Lee, B. et al. First-principles study of the reaction mechanism in sodium–oxygen batteries. Chem. Mater. 26, 1048–1055 (2014).
McCloskey, B. D., Garcia, J. M. & Luntz, A. C. Chemical and electrochemical differences in nonaqueous Li–O2 and Na–O2 batteries. J. Phys. Chem. Lett. 5, 1230–1235 (2014).
Bielski, B. H. J., Cabelli, D. E. & Arudi, R. L. Reactivity of HO2/O2− radicals in aqueous solution. J. Phys. Chem. Ref. Data 14, 1041–1100 (1985).
McCloskey, B. D. et al. On the efficacy of electrocatalysis in Li–O2 batteries. J. Am. Chem. Soc. 133, 18038–18041 (2011).
Sawyer, D. & Valentine, J. S. How super is superoxide? Acc. Chem. Res. 14, 393–400 (1981).
Chin, D.-H., Chiericato, G., Nanni, E. J. & Sawyer, D. T. Proton-induced disproportionation of superoxide ion in aprotic media. J. Am. Chem. Soc. 104, 1296–1299 (1982).
Foote, C. S., Valentine, J. S., Greenberg, A. & Liebman, J. F. (ed.) Active Oxygen in Chemistry (Structure Energetics and Reactivity in Chemistry Series 2, Springer, 1995).
Ernst, S., Aldous, L. & Compton, R. G. The electrochemical reduction of oxygen at boron-doped diamond and glassy carbon electrodes. J. Electroanal. Chem. 663, 108–112 (2011).
Kim, H. C. Progress in Battery 500 Project. in Proc. ILABS 2014 (IBM Research-Almaden Research Center, 2014).
Xie, B. et al. New electrolytes using Li2O or Li2O2 oxides and tris(pentafluorophenyl) borane as boron based anion receptor for lithium batteries. Electrochem. Commun. 10, 1195–1197 (2008).
Shanmukaraj, D. et al. Boron esters as tunable anion carriers for non-aqueous batteries electrochemistry. J. Am. Chem. Soc. 132, 3055–3062 (2010).
Gowda, S. R., Brunet, A., Wallraff, G. M. & McCloskey, B. D. Implications of CO2 contamination in rechargeable nonaqueous Li–O2 batteries. J. Phys. Chem. Lett. 4, 276–279 (2013).
Ganapathy, S. et al. The nature of Li2O2 oxidation in a Li-O2 battery revealed by operando X-ray diffraction. J. Am. Chem. Soc. 136, 16335–16344 (2014).
Mo, Y. F., Ong, S. P. & Ceder, G. First-principles study of the oxygen evolution reaction of lithium peroxide in the lithium–air battery. Phys. Rev. B 84, 1–9 (2011).
The authors acknowledge financial support from NRCan, through the EcoEII programme, and from NSERC, via the Canada Research Chair and Discovery programme (to L.F.N.) and scholarship programme (CGS-D, to R.B. and B.A.). The Waterloo Institute of Nanotechnology is acknowledged for a WIN fellowship to R.F. The authors thank G. Popov for assistance with the Rietveld refinement of pure NaOTf.
The authors declare no competing financial interests.
About this article
Cite this article
Xia, C., Black, R., Fernandes, R. et al. The critical role of phase-transfer catalysis in aprotic sodium oxygen batteries. Nature Chem 7, 496–501 (2015) doi:10.1038/nchem.2260
High Performance Na-O2 Batteries and Printed Microsupercapacitors Based on Water-Processable, Biomolecule-Assisted Anodic Graphene
ACS Applied Materials & Interfaces (2020)
Energy Technology (2020)
Trends in Chemistry (2020)
Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal–O2 batteries
Energy & Environmental Science (2019)
Sodium metal anodes for room-temperature sodium-ion batteries: Applications, challenges and solutions
Energy Storage Materials (2019)