Halogenated Ti3C2 MXene as High Capacity Electrode Material for Li-ion Batteries

doi:10.15541/jim20210550

Abstract

Abstract:

MXenes have been widely studied for their excellent specific surface area, high conductivity and composition tunability, which have been used as a highly efficient electrode material for lithium-ion batteries (LIBs). However, limited storage capacity and severe lattice expansion caused by Li-ions diffusion restrict the application of MXenes as electrode materials. Here, Ti₃C₂ MXenes with surface halogenation (fluorination, chlorination and bromination) as representative MXene materials were designed. Effects of surface functionalization on the atomic structures, electronic properties, mechanical properties, and electrochemical performance of Ti₃C₂T₂ (T = F, Cl and Br) anode in LIBs were investigated using first-principles calculations based on density functional theory with van der Waals correction. The results reveal that Ti₃C₂T₂ MXenes exhibit metallic conductivity with improved structural stability and mechanical strength. Compared with Ti₃C₂F₂ and Ti₃C₂Br₂, Ti₃C₂Cl₂ exhibits the large elastic modulus (321.70 and 329.43 N/m along x and y directions, respectively), low diffusion barrier (0.275 eV), high open circuit voltage (0.54 eV), and storage capacity (674.21 mA·h/g) with stoichiometric ratio of Ti₃C₂Cl₂Li₆, which renders the enhanced rate performance and endures the repeated lattice expansion and contraction during the charge/ discharge process. Moreover, surface chlorination yields expanded interlayer spacing, which can improve Li-ion accessibility and fast charge-discharge rate in Ti₃C₂Cl₂. The research demonstrates that Cl^- terminated Ti₃C₂ is a promising anode material, and provides effective and reversible routes to engineering other MXenes as anode materials for LIBs.

Key words: MXenes, Ti₃C₂, surface end group modification, first-principles calculation, Li-ion battery anode, interlayer spacing

CLC Number:

TM911

XIAO Meixia, LI Miaomiao, SONG Erhong, SONG Haiyang, LI Zhao, BI Jiaying. Halogenated Ti₃C₂ MXene as High Capacity Electrode Material for Li-ion Batteries[J]. Journal of Inorganic Materials, 2022, 37(6): 660-668.

Figures/Tables 12

Fig. 1 Top and side views of M1, M2, M3, and M4 Ti3C2T2 configurations Blue, black and nattier blue balls represent Ti, C and T atoms, respectively, where T denotes F, Cl or Br atoms Colorful views ave arailable on website

Table 1 Formation energy Ef of (eV) Ti3C2T2 with four configurations

Ti₃C₂T₂	M1/eV	M2/eV	M3/eV	M4/eV
Ti₃C₂F₂	-4.23	-4.60	-4.94	-4.77
Ti₃C₂Cl₂	-2.44	-3.07	-3.33	-3.20
Ti₃C₂Br₂	-1.95	-2.57	-2.81	-2.69

Table 2 Lattice parameters a of M3-Ti3C2T2 and corresponding bond lengths of lTi2-T and lTi2-C

Ti₃C₂T₂	a /nm	l_Ti2-T/nm	l_Ti2-C/nm
Ti₃C₂F₂	0.308	0.217	0.208
Ti₃C₂Cl₂	0.319	0.251	0.211
Ti₃C₂Br₂	0.325	0.264	0.213

Fig. 2 Partial density of states (PDOS) and electron density difference of M3-Ti3C2T2 Blue, black and nattier blue balls represent Ti, C and T atoms, respectively, and red- and blue-colored regions indicate electron accumulation and depletion, respectively Colorful figures are available on website

Fig. 3 Strain energy to strain curves of M3-Ti3C2T2 along (a) x- and (b) y-direction, respectively, and (c) elasticmodulus values in x and y directions Blue, black and nattier blue balls represent Ti, C and T atoms, respectively Colorful figures are available on website

Table 3 Adsorption energy (Eab), charge transfer amount (Δq) and adsorption height (Δh), of Liion for stable M3-Ti3C2T2-Li with Liion adsorbed on Ti3C2T2 surface

Ti₃C₂T₂-Li	E_ab/eV	Δq/e	Δh/nm
M3-Ti₃C₂F₂-Li_T2	-1.21	0.61	0.021
M3-Ti₃C₂Cl₂-Li_T1	-0.72	0.40	0.026
M3-Ti₃C₂Br₂-Li_T1	-0.41	0.33	0.028

Fig. 4 Schematic diagram of Li-ion migration path on (a) Ti3C2F2, (b) Ti3C2Cl2 and (c) Ti3C2Br2, and corresponding energy profiles and transition states of Li-ion migration on (d) Ti3C2F2, (e) Ti3C2Cl2 and (f) Ti3C2Br2 surfaces Colorful figures are available on website

Fig. 5 Top and side views of (a) Ti3C2F2, (b) Ti3C2Cl2 and (c) Ti3C2Br2 with the adsorption of multi-layer Liions Blue, black, nattier blue, and purple balls represent Ti, C, T, and Li atoms, respectively. 1 Å=0.1 nm Colorful figures are available on website

Table 4 Average open circuit voltage (OCV), adsorption energies of the Liions on the double (E2nd) and triple (E3rd) layers, and the maximum theoretical capacity (CM) of the multi-layer Li-ion adsorption of M3-Ti3C2T2

Ti₃C₂T₂	OCV_1st/V	OCV_2nd/V	OCV_3rd/V	E_2nd/eV	E_3rd/eV	CM /(mA h·g^-1)
Ti₃C₂F₂	0.57	0.61	-	-5.25	-	521.41
Ti₃C₂Cl₂	0.37	0.53	0.54	-5.48	-4.51	674.21
Ti₃C₂Br₂	0.34	0.51	0.52	-5.39	-4.45	491.14

Fig. 6 Partial density of states (PDOS) of M3-Ti3C2T2 electrode with the maximum adsorption of Liions

Fig. 7 Top and side views of three feasible stacking configurations of double Ti3C2Cl2. Blue, black, green, and purple balls represent Ti, C, T, and Li atoms, respectively; Colorful figures are available on website

Fig. 8 (a) Schematic illustration of the diffusion path of Liion, (b) corresponding energy profiles and configurations of transition states, (c) atomic structures and interlayer distances at initial and transition states of D33-Ti3C2Cl2 during interlayer Li-ion migration. Blue, black and green balls represent Ti, C and T atoms, respectively. 1 Å =0.1 nm; Colorful figures are available on website

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Halogenated Ti₃C₂ MXene as High Capacity Electrode Material for Li-ion Batteries

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