Simple and Scalable Synthesis Method of γ-NaTiOPO4 for Sodium Ion Batteries in Aqueous and Non-Aqueous Electrolytes

Abstract

Lithium-ion batteries have been considered a suitable battery technology for energy storage systems. However, its scarcity and high cost pose challenges to the availability of lithium for mass adoption in large applications such as energy storage. Due to their natural abundance and economic feasibility, sodium-ion batteries (SIBs) have proven to be a promising alternative for large-scale applications.1 Most anode materials for research on SIBs have focused on carbonaceous materials, oxides and polyanionic compounds of the anode, like that of lithium-ion battery research on anode materials Polyanionic compounds, especially phosphates, are of particular interest due to their structural, thermal properties and, more importantly, for avoiding undesirable sodium plating.2 Contrary to lithium counterparts, SIBs have fewer alternatives for safe anode materials applicable for both non-aqueous and aqueous rechargeable SIBs.3 Various NaTiOPO4 polymorphs have previously been reported, and these materials required a synthesis process that was extremely time-consuming and a highly pressured synthesis atmosphere. However, the methods reported still produced very small amounts of synthesized material.4-8 Due to these limitations, only the β-NaTiOPO4 phase among polymorphs was studied as an anode for SIBs in a non-aqueous electrolyte.7-8 In this study, we first report a simple and scalable solid-state synthesis method for γ-NaTiOPO4, which incorporates a high-temperature quenching process to stabilize metastable γ-NaTiOPO4 with stability. It is a promising anode for SIBs in non-aqueous and aqueous electrolytes, with a capacity of roughly 120mAh/g, voltages of 1.7V and 1.5V vs Na/Na +, and a Coulombic efficiency of up to 99.9% for up to 500 cycles at 0.5C in non-aqueous electrolyte and excellent capacity retention in a full cell of NaMn0.44O2//γ-NaTiOPO4 for up to 175 cycles in aqueous electrolyte.9 El Kharbachi, A.; Zavorotynska, O.; Latroche, M.; Cuevas, F.; Yartys, V.; Fichtner, M., Exploits, advances and challenges benefiting beyond Li-ion battery technologies. Journal of Alloys and Compounds 2020, 817.N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Research development on sodium-ion batteries, Chem. Rev. 114 (23) (2014) 11636–11682. H. Kim, J. Hong, K.Y. Park, H. Kim, S.W. Kim, K. Kang, Aqueous rechargeable Li and Na ion batteries, Chem. Rev. 114 (23) (2014) 11788–11827. Stus, N. V.; Slobodyanik, M. S.; Straitiychuk, D. A.; Lisnyak, V. V., Pressure induced gamma ->alpha-NaTiOPO4 phase transition. J Alloy Compd 2005, 393 (1-2), 66-69.Dahaoui, S.; Hansen, N. K.; Protas, J.; Krane, H.-G.; Fischer, K.; Marnier, G., Electric properties of KTiOPO4 and NaTiOPO4 from temperature-dependent X-ray diffraction. Journal of Applied Crystallography 1999, 32 (1), 1-10.Loiacono, G. M.; Loiacono, D. N.; Stolzenberger, R. A., Growth and properties of crystals in the system KTiOPO4-NaTiOPO4. Journal of Crystal Growth 1994, 144 (3), 223-228.Mu, L. Q.; Ben, L. B.; Hu, Y. S.; Li, H.; Chen, L. Q.; Huang, X. J., Novel 1.5 V anode materials, ATiOPO(4) (A = NH4, K, Na), for room -temperature sodium-ion batteries. Journal Jiang, L. W.; Liu, L. L.; Yue, J. M.; Zhang, Q. Q.; Zhou, A. X.; Borodin, O.; Suo, L. M.; Li, H.; Chen, L. Q.; Xu, K.; Hu, Y. S., High-Voltage Aqueous Na-Ion Battery Enabled by Inert-Cation-Assisted Water-in-Salt Electrolyte. Advanced Materials 2020, 32 (2).Kim, D.; Park, H.; Avdeev, M. ; Kim, M. ; Kang, B. (2022). Newly developed γ – NaTiOPO4 by Simple Solid-State Synthesis for Anode Material of Na-ion Batteries in Both Non-aqueous and Aqueous electrolyte. Journal of Power Sources 2022, 541 (1)