Iron and Titanium-Based Electrode Materials for Sodium-Ion Batteries

In the past two decades, lithium-ion batteries (LIBs) have been successfully used in mobile electronic devices. With the development of hybrid electrical vehicles (HEVs), electrical vehicles (EVs), and energy storage stations, etc., of which a battery needs at least manifold amount of lithium, the cost of lithium would be further driven higher as the lithium metal reserves are limited both in amount and geographical location. Recently, sodium-ion batteries (NIBs) have been proven to be the most attracted alternative rechargeable systems for the potential large-scale production because sodium is much cheaper and more abundant in the Earth’s crust, and the potential of sodium metal is only 0.3 V higher than that of lithium. Therefore, it is urgent for us to develop NIBs to provide sufficient low-cost and safe energy storage devices for our society.

  Recent studies in NIBs focused on the development of electrode materials. A number of promising electrode materials, including cathodes such as α-NaFeO₂-based NaMO₂ (M = Fe, Co, Mn, Ni, Ti, etc.) [1, 2], polyanion-based Na₃V₂(PO₄)₃ [3], Na₃MPO₄CO₃ [4], Na₄Fe₃(PO₄)₂(P₂O₇) [5], and Prussian blue [6], and anodes such as hard carbon [7], Na₂Ti₃O₇ [8], P2-type Na_2/3Co_1/3Ti_2/3O₂ [9], and carboxylate-based materials [10] have already been explored for NIBs. The development of feasible electrode materials by an optimized composition with high capacity, long cycle life, and low cost still remains a challenging issue that warrants further investigation. Looking back to the history, iron (Fe) always has the priority being used when it comes to transition metal oxides because the elemental abundance in the Earth’s crust is of primary importance for large-scale batteries [1, 11]. In this pursuit, herein, O3-type Na[Fe_1/3Ni_1/3Ti_1/3]O₂ cathode material and orthorhombic Na_x[FeTi]O₄ (x = 1 and 4/3) anode materials are synthesized by a solid-state reaction method, and studied as a positive electrode and negative electrodes for NIBs, all tested in a half cell and at 20 ºC, using 1 M NaClO₄ in 1:1 weight ratio of propylene carbonate (PC) and dimethyl carbonate (DEC) as electrolyte, and a glass fiber filter (GF/D, Whatman) as separator. The obtained Na[Fe_1/3Ni_1/3Ti_1/3]O₂ cathode material has an initial discharge capacity of 115 mAh g^-1 under a current density of 10 mA g^-1 (0.1 C) in the voltage range of 1.5-4.0 V, and shows reversible discharge capacity values of 91.3, 89.7, 79.2, 69.7, 46.2, and 30.9 mAh g^-1, respectively at 0.2, 0.5, 1, 2, 5, and 10 C. The potentials reported in this work refer to the Na⁺/Na couple. The obtained Na_4/3[FeTi]O₄  anode material exhibits a first charge capacity of 119.6 mAh g^-1 under a current density of 17.7 mA g^-1 (0.1 C) in the voltage range of 0.01-2.5 V, and delivers reversible charge capacity values of 84.5, 73.1, 61.4, 47.5, and 36.7 mAh g^-1, respectively at 0.5, 1, 2, 5, and 10 C. The even more promising thing is as-prepared orthorhombic Na[FeTi]O₄ exhibits an initial charge capacity of about 181 mAh g^-1 at 0.1 C, and good cycling performance as well.

References

[1] N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi, R. Okuyama, R. Usui, Y. Yamada, S. Komaba, Nature  Mater., 11 (2012) 512-517.

[2] D. Buchholz, A. Moretti, R. Kloepsch, S. Nowak, V. Siozios, M. Winter, S. Passerini, Chem. Mater., 25 (2013) 142-148.

[3] Z. L. Jian, W. Z. Han, H. X. Yang, Y. S. Hu, J. Zhou, Z. B. Zhou, J. Q. Li, W. Chen, D. F. Chen, L. Q. Chen, Adv. Energy Mater., 3 (2013) 156-160.

[4] H. L. Chen, G. Hautier, G. Ceder, J. Am. Chem. Soc., 134 (2012) 19619-19627.

[5] H. Kim, I. Park, S. Lee, H. Kim, K. Y. Park, Y. U. Park, H. Kim, J. Kim, H. D. Lim, W. S. Yoon, K. Kang, Chem. Mater., 25 (2013) 3614-3622.

[6] Y. You, X. L. Wu, Y. X. Yin, Y. G. Guo, Energ Environ. Sci., 7 (2014) 1643-1647.

[7] D. A. Stevens, J. R. Dahn, J. Electrochem. Soc., 147 (2000) 1271-1273.

[8] P. Senguttuvan, G. Rousse, V. Seznec, J. M. Tarascon, M. R. Palacín, Chem. Mater., 23 (2011) 4109-4111.

[9] H. J. Yu, Y. Ren, D. D. Xiao, S. H. Guo, Y. B. Zhu, Y. M. Qian, L. Gu, H. S. Zhou, Angew. Chem., 53 (2014) 8963-8969.

[10] L. Zhao, J. M. Zhao, Y. S. Hu, H. Li, Z. B. Zhou, M. Armand, L. Q. Chen, Adv. Energy Mater., 2 (2012) 962-965.

[11] P. Barpanda, G. Oyama, S. I. Nishimura, S. C. Chung, A. Yamada, Nature Comm., DOI: 10.1038/ncomms5358.

Figure 1. Electrochemical properties of the obtained NaFe_1/3Ni_1/3Ti_1/3O₂ cathode material and Na_4/3[FeTi]O₄ anode material.