Multinuclear Solid-State NMR Studies of Cathode Materials for Lithium and Sodium Ion Batteries

Lithium ion batteries have long been promised as an alternative energy technology, owing to their high volumetric and gravimetric energy densities.¹ The cathode (positive electrode) material is of particular importance as the choice of this component can dictate overall battery performance.  Polyanionic structural frameworks such as phosphates or fluorosulfates are an attractive alternative to the traditional layered oxide cathode structures due to their high electrochemical and thermal stability.² More recently, the reconsideration of sodium ion batteries has become popular, and while the larger, heavier, sodium ion decreases overall energy density for a given material vs. Li, the cost and abundance benefits are expected to largely outweigh this disadvantage.³ Despite considerable research efforts to improve cathode materials for both lithium and sodium ion batteries, the role of structure on ion mobility is not yet fully understood; a property integral to electrochemical success.

Solid-state nuclear magnetic resonance (ssNMR) is a valuable tool for studying these polyanionic structures, as it is sensitive to both the mobile ion of interest (²³Na or ⁶Li/⁷Li) as well as the surrounding structural framework (³¹P, ¹⁹F).  The fluorophosphate family of sodium cathode materials is extremely promising, as the materials are both thermally and electrochemically stable, with the advantage of being relatively inexpensive depending on the redox active transition metal of choice. In particular, the electrochemical performance of Na₂MPO₄F (M= Fe, Co, Ni, Mn) has been investigated in recent years, and is found to be an exemplary candidate for use in Na ion batteries.⁴ We have utilized ²³Na NMR to gain understanding of the structural changes that occur during electrochemical extraction and reinsertion of Na ions during the charging and discharging processes of a number of fluorophosphate analogues. The paramagnetic nature of many of these materials makes their investigation by NMR non-trivial, requiring the use of fast magic-angle spinning (MAS) and low external magnetic fields.  In particular, the structural changes occurring upon desodiation of Na₂FePO₄F were investigated by NMR, where the attenuation of one of the two sites is attributed to the selective removal of Na ions from a single crystallographic position.  Additionally, by cycling Na₂FePO₄F versus a Li-metal counter electrode we observe evidence of substantial Na-Li ion exchange by ⁷Li NMR, opening the door for interesting heteronuclear correlation experiments with a hybrid Na/Li cathode material.  

The movement of Li ions as a function of electrochemical cycling can also be tracked in Li cathode materials. Receiving significant attention is the fluorosulfate structure of the form LiFeSO₄F, which benefits from a high redox potential and excellent electrochemical behaviour.^{5,6 6,7}Li ssNMR was used here to identify any changes to the Li environment at various stages along the electrochemical charge/discharge cycle, providing valuable insight into the structural stability of this material.

(1) Tarascon, J.-M.; Armand, M. Nature 2001. (2) Padhi, A. K.; Nanjundaswamy, K. S.; Masquelier, C.; Masque; Okada, S.; Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1609–1613. (3) Ellis, B. L.; Nazar, L. F. Current Opinion in Solid State & Materials Science 2012, 16, 168–177. (4) Ellis, B. L.; Makahnouk, W. R. M.; Rowan-Weetaluktuk, W. N.; Ryan, D. H.; Nazar, L. F. Chem. Mater. 2010, 22, 1059–1070. (5) Barpanda, P.; Ati, M.; Melot, B. C.; Rousse, G.; Chotard, J.-N.; Doublet, M.-L.; Sougrati, M. T.; Corr, S. A.; Jumas, J.-C.; Tarascon, J.-M. Nature Materials 2011, 10, 772–779. (6) Tripathi, R.; Gardiner, G. R.; Islam, M. S.; Nazar, L. F. Chem. Mater. 2011, 23, 2278–2284.

Figure 1: ²³Na 30 kHz MAS NMR spectra of pristine Na₂FePO₄F (red) and electrochemically generated Na_1.5FePO₄F (blue) demonstrating the decrease in intensity at site A during cycling as well as the formation of a novel site (#).