Rate and Cycling Performance of Ti and Cu Doped β-NaMnO2 as Cathode of Sodium-ion Battery

doi:10.15541/jim20240204

Abstract

Abstract:

Sodium-ion batteries are economical and environmentally sustainable energy storage batteries. Among them, β-NaMnO₂, a promising sodium-ion cathode material, is a manganese-based oxide with a corrugated laminar structure, which has attracted significant attention due to its structural robustness and relatively high specific capacity. However, it has short cycle life and poor rate capability. To address these issues, Ti atoms, known for enhancing structural stability, and Cu atoms, which facilitate desodiation, were doped into β-NaMnO₂by first-principles calculation and crystal orbital Hamilton population (COHP) analysis. β-NaMn_0.8Ti_0.1Cu_0.1O₂ exhibits a notable increase in reversible specific capacity and remarkable rate properties. Operating at a current density of 0.2C (1C = 219 mA·g^-1) and within a voltage range of 1.8-4.0 V, the modified material delivers an initial discharge capacity of 132 mAh·g^-1. After charge/discharge testing at current densities of 0.2C, 0.5C, 1C, 3C, and 0.2C, the material still maintains a capacity of 110 mAh·g^-1. The doping of Ti atoms slows down the changes in the crystal structure, resulting in only minimal variation in the lattice constant c/a during the desodiation process. Mn and Cu engage in reversible redox reactions at voltages below 3.0 V and around 3.5 V, respectively. The extended plateau observed in the discharge curve below 3.0 V signifies that Mn significantly contributes to the overall battery capacity. This study provides insights into modifying β-NaMnO₂ as a cathode material, offering experimental evidence and theoretical guidance for enhancing battery performance in Na-ion batteries.

Key words: first-principles, sodium-ion battery, layered cathode material

CLC Number:

TQ174

ZHOU Jingyu, LI Xingyu, ZHAO Xiaolin, WANG Youwei, SONG Erhong, LIU Jianjun. Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery[J]. Journal of Inorganic Materials, 2024, 39(12): 1404-1412.

Figures/Tables 14

Fig. 1 Screening of doped atoms in β-NaMnO2 (a) Schematic crystal structure of β-NaMnO2 doped by 3d transition metal atoms; (b) -ICOHP of Na-O and TM-O (TM=Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn); (c) -COHP of Na-O and Cu-O in Cu doped β-NaMnO2; (d) -COHP of Na-O and Ti-O in Ti doped β-NaMnO2. Colorful figures are available on website

Fig. 2 Structure and morphology of β-MTC811 (a) Crystal structure modeling of β-MTC811 that obtained by calculation; (b) Comparison of calculated and experimental XRD patterns of β-MTC811; (c) SEM image of β-MTC811; (d) EDS mappings of β-MTC811; (e) TEM image of β-MTC811; (f) Enlarged image of zig-zag layered structure in (e)

Fig. 3 Electrochemical performance of β-MTC811 cathode (a-c) Charge/discharge curves of (a) β-MTC811, (b) β-MTC721 and (c) β-MTC712 at 0.2C; (d) Cycling performance, (e) rate performance and (f) dQ/dV curves of β-MTC811 Colorful figures are available on website

Fig. 4 Electrochemical reaction mechanisms (a) Mn2p and (b) Cu2p XPS spectra of β-MTC811 in different charging and discharging states. Colorful figures are available on website

Fig. 5 First-principles calculations of β-MTC811 cathode (a) Schematic diagram of desodiation process; (b) Lattice constant c/a during desodiation; (c) Calculated and fitted voltage plateaus, and experimental voltage curve; (d) Bader charge of Mn and Cu; (e-g) pDOS of Mn3d and Cu3d during different desodiation processes Colorful figures are available on website

Fig. S1 -COHP of Na-O (O from Na-O-TM) (TM=Co, Cu, V, Cr, Ni, Fe, Mn, Zn, Ti) in doped β-NaMnO2

Fig. S2 -COHP of TM-O (TM=Mn, Zn, Ti, V, Cr, Fe, Co, Ni, Cu) in doped β-NaMnO2

Fig. S3 XRD patterns of β-MTC811, β-MTC721 and β-MTC712

Fig. S4 Crystal-structure modelings of (a, b) β-MTC712 and (c, d) β-MTC721

Fig. S5 Electrochemical performance of (a-c) β-MTC721 and (d-f) β-MTC712 cathodes (a, d) Cycling performance during 50 cycles; (b, e) rate performance; (c, f) dQ/dV curves

Fig. S6 CV curves of β-MTC811

Table S1 Bond lengths of Na-O (in Na-O-TM) and TM-O

Element	Na-O/Å	TM-O/Å
Ti	2.37641	1.95505
V	2.32810	1.98783
Cr	2.36871	1.98479
Mn	2.33621	1.97821
Fe	2.34627	2.00070
Co	2.36626	1.94259
Ni	2.35691	1.91536
Cu	2.39119	1.98934
Zn	2.36493	2.08207

Table S2 ICP-OES results of β-MTC811, β-MT712 and β-MTC721

Sample	Measured atomic ration
Sample	Mn	Ti	Cu
β-MTC811	0.8	0.09	0.1
β-MTC712	0.7	0.08	0.2
β-MTC721	0.7	0.19	0.1

Table S3 Parameters for button cell batteries

Material	Cathodes’ mass loading/mg	Electrolyte amount/μL	Radius/mm
β-MTC811	4.192	160	14
β-MTC721	4.360	160	14
β-MTC712	5.696	160	14

References 35

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Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery

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