Transport Properties and SEI Stability of Na2Ti3O7 electrodes for Na-Ion Batteries: An EIS Study

Na2Ti3O7 is a promising negative electrode for Na-ion batteries (NIBs) with a very low insertion voltage (0.3 V vs. Na+/Na) and high specific capacity (178 mAh/g) [1, 2]. However, Na2Ti3O7 shows poor capacity retention when synthesized from Na2CO3 as sodium precursor, reaching only 50-70% of capacity retention after 10 cycles [3, 4, 5]. The capacity fading is correlated, among other factors, with the presence of Na2CO3 on the particles [3], which is originated by the interaction of Na2Ti3O7 particles with atmospheric H2O and CO2. Another important factor to take into account is the formation of a stable solid-electrolyte interphase (SEI) layer. In fact, the reversible Na+ insertion/extraction reaction occurs at low potential and, therefore, electrolyte reduction occurs. The stability and composition of this SEI layer has been previously studied by X-ray photoelectron spectroscopy (XPS) [6], concluding that the SEI layer formed upon Na+insertion is partially dissolved during extraction. In order to better understand the reasons behind the poor capacity retention, an electrochemical impedance spectroscopy (EIS) study was carried out to determine the electronic and ionic transport properties of Na2Ti3O7 electrodes. An interesting change of transport properties, and particularly of electron conductivity, during Na+ insertion/extraction process is revealed for Na2Ti3O7negative electrodes by EIS. Na2Ti3O7 was synthesized via a ceramic route from precursors: TiO2 anatase and Na2CO3·H2O in excess. Three electrode Swagelok type cells were tested using metallic sodium disks as counter and reference electrodes; electrochemical measurements were performed at room temperature in the voltage window 0.05-1.6 V vs. Na+/Na. EIS measurements were performed by controlling the electrode potential through PITT (potentiostatic intermittent titration technique). The EIS study here presented is the first experimental demonstration of a transition from electronic insulator to conductor in Na2Ti3O7 electrodes for NIBs [Fig. 1]. This reversible transition is originated by Na+ insertion/extraction and was recently predicted by DFT calculations. Moreover, the instability of the SEI layer has been also observed, in agreement with previous XPS studies, contributing to the capacity fading widely reported for this material. This confirms that prior to Na+ insertion the Na2Ti3O7 is an insulator and the ionic transport kinetics are limited by the electronic conductivity, but when the intercalated Na+ increases the Na2Ti3O7behaves as a metallic conductor and the kinetics are limited by the interfacial charge-transfer step. Acknowledgments M. Zarrabeitia thanks the Government of the Basque Country for funding through a PhD Fellowship. Financial support from the Basque Government (Etortek 10 CIC Energigune) and from the Ministerio de Economía y Competitividad of the Spanish Government (ENE2013-44330-R) is also acknowledged. References [1] P. Senguttuvan, G. Rousse, V. Seznec, J.M. Tarascon, M. R. Palacín. Chem. Mater. 23, 4109 (2011). [2] G. Rousse, M.E. Arroyo y De Dompablo, P. Senguttuvan, A. Ponrouch, J.M. Tarascon, M.R. Palacín. Chem. Mater. 25, 4946 (2013). [3] M. Zarrabeitia, E. Castillo-Martínez, J.M. López Del Amo, A. Eguía-Barrio, M.A. Muñoz-Márquez, T. Rojo, M. Casas-Cabanas. Acta Materialia, doi: 10.1016/j.actamat.2015.11.033. [4] H. Pan, X. Lu, X. Yu, Y.S. Hu, H. Li, X.Q. Yang, L. Chen. Adv. Energy Mater. 3, 1186 (2013). [5] J. Xu, C. Ma, M. Balasubramanian, Y.S. Meng. Chem. Comm. 50, 12564 (2014). [6] M.A. Muñoz-Márquez, M. Zarrabeitia, E. Castillo-Martínez, A. Eguía-Barrio, T. Rojo, M. Casas-Cabanas. ACS Appl. Mater. Interfaces 7, 7801 (2015)