Fe 3+-stabilized Ti3C2Tx MXene enables ultrastable Li-ion storage at low temperature

doi:10.1016/j.jmst.2020.06.037

Abstract

Abstract:

It is highly important to develop ultrastable electrode materials for Li-ion batteries (LIBs), especially in the low temperature. Herein, we report Fe ³⁺-stabilized Ti₃C₂T_x MXene (donated as T/F-4:1) as the anode material, which exhibits an ultrastable low-temperature Li-ion storage property (135.2 mA h g ^-1 after 300 cycles under the current density of 200 mA g ^-1 at -10 °C), compared with the negligible capacity for the pure Ti₃C₂T_x MXene (~26 mA h g ^-1 at 200 mA g ^-1). We characterized as-made T/F samples via the X-ray photoelectron spectroscopy (XPS), Fourier transformed infrared (FT-IR) and Raman spectroscopy, and found that the terminated functional groups (-O and -OH) in T/F are Li ⁺ storage sites. Fe ³⁺-stabilization makes -O/-OH groups in MXene interlayers become active towards Li ⁺, leading to much more active sites and thus an enhanced capacity and well cyclic stability. In contrast, only -O/-OH groups on the top and bottom surfaces of pure Ti₃C₂T_x MXene can be used to adsorb Li ⁺, resulting in a low capacity. Transmission electron microscopy (TEM) and XPS data confirm that T/F-4:1 holds the highly stable solid electrolyte interphase (SEI) layer during the cycling at -10 °C. Density functional theory (DFT) calculations further uncover that T/F has fast diffusion of Li ⁺ and consequent better electrochemical performances than pure Ti₃C₂T_x MXene. It is believed that the new strategy used here will help to fabricate advanced MXene-based electrode materials in the energy storage application.

Key words: Ti₃C₂Tx MXene, Li-ion storage, Low temperature, Solid electrolyte interphase, Density functional theory

Nana Zhao, Fengchu Zhang, Fei Zhan, Ding Yi, Yijun Yang, Weibin Cui, Xi Wang. Fe ³⁺-stabilized Ti₃C₂T_x MXene enables ultrastable Li-ion storage at low temperature[J]. J. Mater. Sci. Technol., 2021, 67: 156-164.

Figures/Tables 7

Fig. 1. Schematic illustration of the preparation process of T/F.

Fig. 2. (a) XRD patterns of parent Ti3AlC2, pure Ti3C2Tx MXene, T/F-4:1 and α -Fe2O3, respectively. (b) SEM image of T/F-4:1. (c, d) TEM image and corresponding SAED pattern of T/F-4:1, respectively.

Fig. 3. (a) XPS survey spectra of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1, respectively. (b) High-resolution XPS spectrum of O 1s of pure Ti3C2Tx MXene and T/F-4:1, respectively. (c) Raman spectra of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1, respectively. (d) FT-IR spectra of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1, respectively.

Fig. 4. (a) CV curves of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1 at 0.2 mV s-1 at -10 °C, respectively. (b) Galvanostatic charge/discharge profiles of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1 at 200 mA g-1 at -10 °C. (c) Rate performances of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1 at -10 °C. (d) EIS spectra of pure Ti3C2Tx MXene, Fe2O3 and T/F-4:1 at -10 °C (inset shows the pattern of equivalent circuit of EIS spectra for T/F-4:1 electrode). (e) Cycling performances and the corresponding coulombic efficiencies of pure Ti3C2Tx MXene, Fe2O3, T/F-4:1, T/F-2:1 and T/F-1:2 at 200 mA g-1 after 300 cycles at -10 °C, respectively.

Fig. 5. (a-c) TEM image and high-resolution XPS spectra of O 1s and Li 1s of pure Ti3C2Tx MXene electrode after 300 cycles at -10 °C, respectively. (d-f) TEM image and high-resolution XPS spectra of O 1s and Li 1s of T/F-4:1 after 300 cycles at -10 °C, respectively.

Fig. 6. ——(a) Side view of Ti3C2 with -O functional groups. (b) Energy variation of Li diffusion (inset shows the minimal diffusion path) in Ti3C2O2 and T-O/F, respectively. (c) Side view of Ti3C2 with -OH functional groups. (d) Energy variation of Li diffusion (inset shows the minimal diffusion path) in Ti3C2(OH)2 and T-OH/F, respectively.

Fig. 7. Schematic illustration of Li+ insertion process in pure Ti3C2Tx MXene and T/F at -10 °C, respectively.

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Fe ³⁺-stabilized Ti₃C₂T_x MXene enables ultrastable Li-ion storage at low temperature

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