On Synthesis and Electrochemical Performance of Na4Fe3(PO4)2(P2O7) Cathode for Sodium-Ion Batteries

Developing cost-effective and large-scale energy storage systems (ESSs) has been an important topic over the past years in order to implement efficient utilization of renewable electricity generated from sources like solar, wind, geothermal and tidal energy (1). Since the commercialization in 1991, lithium-ion batteries (LIBs) have been widely used in portable electronics, electric vehicles (EVs), and energy storage devices (2). However, there is an increase in demand for alternative energy sources based on abundant and low-cost materials due to the limited reserves and high costs of lithium compounds. In this context, sodium-ion batteries (SIBs) have received great attention because of their similarities to LIBs and the large abundance (2.3%) on earth, and low cost of sodium compounds (3). However, the energy density of most SIBs are lower that of LIBs, primarily due to the larger ionic radius and higher mass of Na + ion compared to Li + ions, as well as the lower electrochemical potential of sodium cells relative to lithium cells (4). Many efforts have been devoted to the development of high-performance cathode materials, including layered transition metal oxides, Prussian blue analogues (PBAs), sulfates, phosphates and pyrophosphates. Polyanionic compounds, in particular, are considered as promising cathode materials with regard to their high working voltage, structural stability, thermal stability and small volume change upon cycling (5). For example, iron phosphate-based materials have gained attention inspired by LiFePO 4 for LIBs. However, the olivine NaFePO 4 is predominantly produced through an ion exchange process (6). The maricite NaFePO 4 is electrochemically inactive due to the lack of Na migration channels within its structure. On the other hand, Na 2 FeP 2 O 7 shows long cycle life and structural stability with a low capacity because of its single electron diffusion process. Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) (NFPP) combines the benefits of both phosphate and pyrophosphate, offering potential advantages such as low-cost, environmental friendliness, high average working voltage (~ 3.1 V vs. Na + /Na), favorable theoretical capacity (129 mAh g -1 ), low volume change (< 4%) due to its open framework composed of [Fe 3 P 2 O 13 ] layers connected by (P 2 O 7 ) 4- groups with 3D ion channels and low activation barriers for Na + transport as well as structural and thermal stability. However, NFPP is susceptible to the formation of impurities such as NaFePO 4 and Na 2 FeP 2 O 7 , which can arise from the synthesis temperature and adopted reaction materials, potentially restricting the electrochemical performance of NFPP. Additionally, the inherent insulating characteristics of the (PO 4 ) 3- group in NFPP may result in reduced electronic conductivity and slow ion diffusion, which hinders its practical application (7, 8). Therefore, various strategies have been developed to enhance conductivity such as nanosizing, carbon coating and metal ion doping. NFPP can be synthesized by various methods like solid-state, sol-gel, spray drying and combustion. In this study, we present our results on employing both sol–gel and combustion methods with distinct synthesis parameters. The structure, morphology and particle size of NFPP are characterized by X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) techniques. The electrochemical performance of NFPP cathodes is investigated in both half- and full-cells via galvanostatic charge-discharge cycling tests. Keywords: sodium-ion batteries, cathode material, iron-based mixed phosphate, sol-gel synthesis, large scale M. Armand and J. M. Tarascon, Nature , 451 , 652 (2008). J. B. Goodenough and K.-S. Park, Journal of the American Chemical Society , 135 , 1167 (2013). B. Dunn, H. Kamath and J.-M. Tarascon, Science , 334 , 928 (2011). M. H. Han, E. Gonzalo, G. Singh and T. Rojo, Energy & Environmental Science , 8 , 81 (2015). P. Barpanda, L. Lander, S.-i. Nishimura and A. Yamada, Advanced Energy Materials , 8 , 1703055 (2018). K. T. Lee, T. N. Ramesh, F. Nan, G. Botton and L. F. Nazar, Chemistry of Materials , 23 , 3593 (2011). X. Wu, G. Zhong and Y. Yang, Journal of Power Sources , 327 , 666 (2016). H. Kim, I. Park, S. Lee, H. Kim, K.-Y. Park, Y.-U. Park, H. Kim, J. Kim, H.-D. Lim, W.-S. Yoon and K. Kang, Chemistry of Materials , 25 , 3614 (2013).