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

材料科学与技术 ›› 2019, Vol. 35 ›› Issue (6): 994-1002.DOI: 10.1016/j.jmst.2018.12.021

收稿日期:2018-09-20 修回日期:2018-11-16 接受日期:2018-11-26 出版日期:2019-06-20 发布日期:2019-06-19

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

Bozhou Chen^a^b, Bangchuan Zhao^a^*(), Jiafeng Zhou^a^b, Zhitang Fang^a^b, Yanan Huang^a, Xuebin Zhu^a, Yuping Sun^a^c

^aKey Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China
^bUniversity of Science and Technology of China, Hefei, 230026, China
^cHigh Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei, 230031, China

Received:2018-09-20 Revised:2018-11-16 Accepted:2018-11-26 Online:2019-06-20 Published:2019-06-19
Contact: Zhao Bangchuan
About author:
¹ These authors contributed equally to this work.

摘要/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

. [J]. 材料科学与技术, 2019, 35(6): 994-1002.

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.

图/表 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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