Surface modification with oxygen vacancy in Li-rich layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 for lithium-ion batteries

doi:10.1016/j.jmst.2018.12.021

Abstract

Abstract:

A couple of layered Li-rich cathode materials Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ without any carbon modification are successfully synthesized by solvothermal and hydrothermal methods followed by a calcination process. The sample synthesized by the solvothermal method (S-NCM) possesses more homogenous microstructure, lower cation mixing degree and more oxygen vacancies on the surface, compared to the sample prepared by the hydrothermal method (H-NCM). The S-NCM sample exhibits much better cycling performance, higher discharge capacity and more excellent rate performance than H-NCM. At 0.2 C rate, the S-NCM sample delivers a much higher initial discharge capacity of 292.3 mAh g^-1 and the capacity maintains 235 mAh g^-1 after 150 cycles (80.4% retention), whereas the corresponding capacity values are only 269.2 and 108.5 mAh g^-1 (40.3% retention) for the H-NCM sample. The S-NCM sample also shows the higher rate performance with discharge capacity of 118.3 mAh g^-1 even at a high rate of 10 C, superior to that (46.5 mAh g^-1) of the H-NCM sample. The superior electrochemical performance of the S-NCM sample can be ascribed to its well-ordered structure, much larger specific surface area and much more oxygen vacancies located on the surface.

Key words: Li-rich cathode oxide material, Oxygen vacancy, Solvothermal method, Electrochemical performance

Bozhou Chen, Bangchuan Zhao, Jiafeng Zhou, Zhitang Fang, Yanan Huang, Xuebin Zhu, Yuping Sun. Surface modification with oxygen vacancy in Li-rich layered oxide Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ for lithium-ion batteries[J]. J. Mater. Sci. Technol., 2019, 35(6): 994-1002.

Figures/Tables 11

Fig. 1. Schematic diagram of preparation process of S-NCM and H-NCM materials.

Fig. 2. XRD patterns of (a) Li1.2Mn0.54Ni0.13Co0.13O2 precursors, (b) Li1.2Mn0.54Ni0.13Co0.13O2 powders, and (c) Raman spectra of S-NCM and H-NCM materials.

Table 1 Structure and morphology parameters of S-NCM and H-NCM samples.

Sample	a (?)	c (?)	c/a	I₍₀₀₃₎/I₍₁₀₄₎	Surface area (m2 g-1)	Pore volume (cc g-1)
H-NCM	2.9134	14.3109	4.912	1.31	4.606	0.007
S-NCM	2.8729	14.3201	4.985	1.47	6.39	0.015

Fig. 3. XPS spectra of (a) Mn 2p, (b) Co 2p, (c) Ni 2p and (d) O 1 s for S-NCM and H-NCM materials.

Fig. 4. SEM images of (a) H-NCM precursors, (b) S-NCM precursors, (c) H-NCM powders, (d) S-NCM powders, (e, f) TEM and (g, h) HRTEM images of (e, g) H-NCM and (f, h) S-NCM samples (d: lattice fringe spacing).

Fig. 5. (a) Initial charge and discharge profiles for S-NCM and H-NCM electrodes, dQ/dV plots of (b) S-NCM and (c) H-NCM samples at 0.2 C rate between 2.0 and 4.8 V.

Fig. 6. (a) Average discharge voltage, discharge voltage profiles from galvanostatic cycling of (b) S-NCM and (c) H-NCM.

Fig. 7. (a) Cycling stability at 0.2 C rate and (b) rate performances of S-NCM and H-NCM electrodes.

Fig. 8. Electrochemical performance of S-NCM electrode compared to LMNCO samples [12,17,20,22,28,39,40].

Fig. 9. (a) Electrochemical impedance spectroscopy and (b) relationship between Z’ and ω-1/2 for S-NCM and H-NCM electrodes (Z’: real part of the impendence; Z’’ imaginary part of the impendence; CPE: double layer capacitance; Zw: Warburg impendence; ω: frequency).

Table 2 Electrochemical parameters obtained from RIS fitting (Cich/Cidch: initial charge/discharge capacities; Cirl: irreversible capacity loss; Qi: initial coulomb efficiency).

Sample	C_ich(mAh g^-1)	C_idh(mAh g^-1)	C_irl(mAh g^-1)	Q_i (%)	R_s(Ω)	R_ct(Ω)	σ	D_Li⁺(cm² s^-1)
H-NCM	346	269.2	76.8	87.5	1.92	345.8	100.3	2.48 × 10^-16
S-NCM	334	292.3	41.7	77.8	4.51	243.3	230.7	1.32 × 10^-15

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Surface modification with oxygen vacancy in Li-rich layered oxide Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ for lithium-ion batteries

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