Formation mechanism; High temperature XRD; Na2Ti3O7; Spray-drying synthesis; Na-ion batteries
Abstract :
[en] Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+. Building a clearer picture of its formation from cheap Na2CO3 and TiO2 starting materials is therefore of obvious interest. Here, we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800 °C, complemented by ex-situ characterizations. We were thereby able to position the previously reported Na4Ti5O12 and Na2Ti6O13 intermediate phases in a reaction scheme involving three successive steps and temperature ranges. Shifts and/or broadening of a subset of the Na2Ti6O13 reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers. This in-situ study was carried out on reproducible mixtures of Na2CO3 and TiO2 in 1:3 molar ratio prepared by spray-drying of mixed aqueous suspensions. Single-phase Na2Ti3O7 was obtained after only 8 h at 800 °C in air, instead of a minimum of 20 h for a conventional solid-state route using the same precursors. Microstructure analysis revealed ~ 15 µm diameter granules made up from rectangular rods of a few-µm length presenting electrochemical properties in line with expectations. In the absence of grinding or formation of intimate composites with conductive carbon, the specific capacity of 137 mAh/g at C/5 decreased at higher rates.
Disciplines :
Chemistry
Author, co-author :
Piffet, Caroline ; Université de Liège - ULiège > Département de chimie (sciences) > LCIS - GreenMAT
Vertruyen, Bénédicte ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie inorganique structurale
Hatert, Frédéric ; Université de Liège - ULiège > Département de géologie > Minéralogie et cristallochimie
Cloots, Rudi ; Université de Liège - ULiège > Département de chimie (sciences) > Vice-Recteur à la vie étud. et aux infrastr. immobilières
Perveen, T., Siddiq, M., Shahzad, N., Ihsan, R., Ahmad, A., Shahzad, M.I., Renew. Sustain. Energy Rev., 119, 2020, 109549.
Li, F., Zhou, Z., Small 14 (2018), 1–25.
Ellis, B.L., Nazar, L.F., Curr. Opin. Solid State Mater. Sci. 16 (2012), 168–177.
Nita, C., Zhang, B., Dentzer, J., Matei Ghimbeu, C., J. Energy Chem. 58 (2021), 207–218.
Yabuuchi, N., Kubota, K., Dahbi, M., Komaba, S., Chem. Rev. 114 (2014), 11636–11682.
Hasa, I., Mariyappan, S., Saurel, D., Adelhelm, P., Koposov, A.Y., Masquelier, C., Croguennec, L., Casas-Cabanas, M., J. Power Sources, 482, 2021, 228872.
Du, K., Rudola, A., Balaya, P., Appl, A.C.S., Mater. Interfaces 13 (2021), 11732–11740.
Zhai, H., Xia, B.Y., Park, H.S., J. Mater. Chem. A 7 (2019), 22163–22188.
Que, L.-F., Yu, F.-D., Deng, L., Gu, D.-M., Wang, Z.-B., Energy Storage Mater. 25 (2020), 537–546.
Muñoz-Márquez, M.A., Zarrabeitia, M., Castillo-Martínez, E., Eguía-Barrio, A., Rojo, T., Casas-Cabanas, M., Appl, A.C.S., Mater. Interfaces 7 (2015), 7801–7808.
Zarrabeitia, M., Castillo-Martínez, E., Lopez Del Amo, J.M., Eguía-Barrio, A., Munoz-Marquez, M.A., Rojo, T., Casas-Cabanas, M., Acta Mater. 104 (2016), 125–130.
Zarrabeitia, M., Nobili, F., Munoz-Marquez, M.A., Rojo, T., Casas-Cabanas, M., J. Power Sources 330 (2016), 78–83.
Torres-Martínez, L.M., Juárez-Ramírez, I., Del Ángel-Sánchez, K., Garza-Tovar, L., Cruz-López, A., Del Ángel, G., J. Sol-Gel Sci. Technol. 47 (2008), 158–164.
Araújo-filho, A.A., Silva, F.L.R., Righi, A., Mauricélio, B., Silva, P., Caetano, E.W.S., Freire, V.N., J. Solid State Chem. 250 (2017), 68–74.
Zarrabeitia, M., Castillo-Martínez, E., López Del Amo, J.M., Eguía-Barrio, A., Muñoz-Márquez, M.A., Rojo, T., Casas-Cabanas, M., J. Power Sources 324 (2016), 378–387.
Zukalová, M., Lásková, B.P., Mocek, K., Zukal, A., Bouša, M., Kavan, L., J. Solid State Electrochem. 22 (2018), 2545–2552.