Synthesis and Properties of Mg‑Doped Ni‑Rich Ternary Cathode Material LiNi0.90Co0.05Mn0.05O2

doi:10.19894/j.issn.1000-0518.230291

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (4): 568-576.DOI: 10.19894/j.issn.1000-0518.230291

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Synthesis and Properties of Mg‑Doped Ni‑Rich Ternary Cathode Material LiNi_0.90Co_0.05Mn_0.05O₂

Sheng CHEN², Zu-Fei HU², Hong-Mei CAO³, Zhen-Hua ZHAO¹, Yu-Dong ZHANG¹()

^1.School of Materials Science and Engineering，Jiangsu University of Science and Technology，Zhenjiang 212100，China
^2.Hunan Jiuri New Materials Co. ，Ltd. ，Huaihua 418200，China
^3.School of Energy and Power，Jiangsu University of Science and Technology，Zhenjiang 212100，China

Received:2023-09-23 Accepted:2024-02-02 Published:2024-04-01 Online:2024-04-28
Contact: Yu-Dong ZHANG
About author:yudongzhang@just.edu.cn
Supported by:
Hunan Science and Technology Association “Xiaohe” Science and Technology Talent Lifting Project(2023TJ?X92)

Abstract

Abstract:

A series of Mg-doped LiNi_0.90Co_0.05Mn_0.05O₂ cathode materials are synthesized via a high-temperature solid-phase method. The phase structure， particle morphology， and electrochemical properties of the doped LiNi_0.90Co_0.05Mn_0.05O₂ cathode materials are investigated using the X-ray diffraction， scanning electron microscope， transmission electron microscope， and X-ray photoelectron spectroscopy. The test results demonstrate that while Mg doping reduces the reversible capacity of the cathode， it expands the lattice volume， inhibits irreversible phase transitions， improves electrode-electrolyte interface stability， and effectively enhances cycle stability. Among the samples， the LiNi_0.90Co_0.05Mn_0.05O₂ cathode material with 3% Mg molar doping amount exhibits a stable structure with less capacity loss and superior overall performance. The discharge specific capacity of the sample at the first cycle reaches 197.3 mA?h/g at 0.1 C in the voltage range of 2.8~4.3 V. Furthermore， it achieves a remarkable cycle retention rate of 93.6% after 100 cycles and maintains a high discharge specific capacity at 5 C （161.1 mA?h/g）.

Key words: Lithium-ion batteries, Cathode materials, Element doping, Electrochemical performance

CLC Number:

O646.5

Sheng CHEN, Zu-Fei HU, Hong-Mei CAO, Zhen-Hua ZHAO, Yu-Dong ZHANG. Synthesis and Properties of Mg‑Doped Ni‑Rich Ternary Cathode Material LiNi_0.90Co_0.05Mn_0.05O₂[J]. Chinese Journal of Applied Chemistry, 2024, 41(4): 568-576.

Figures/Tables 13

Fig.1 XRD spectra of LiNi0.90Co0.05Mn0.05O2 cathode materials doped with different contents of Mg

Fig.2 Refined XRD spectra of LiNi0.90Co0.05Mn0.05O2 cathode materials doped with different contents of Mg

Table 1 The cell parameters of each cathode material obtained by refinement

Sample	a/nm	c/nm	V/nm³	c/a	I_（003）/I_（104）
NCMMg?0	0.287 705	1.420 487	0.101 827	4.937 3	1.885
NCMMg?1	0.287 832	1.420 928	0.101 949	4.936 6	1.745
NCMMg?3	0.287 965	1.421 538	0.102 087	4.936 5	1.771
NCMMg?5	0.287 921	1.421 426	0.102 047	4.936 8	1.667
NCMMg?7	0.288 038	1.421 963	0.102 169	4.936 7	1.567

Fig.3 SEM images of （A） Ni0.90Co0.05Mn0.05（OH）2 precursor and cathode materials （B） NCAMMg-0，（C） NCAMMg-1，（D） NCAMMg-3，（E） NCAMMg-5，（F） NCAMMg-7， and （G） EDS spectra of NCAMMg-3

Table 2 The proportion of Ni， Co， Mn and Mg elements in each sample obtained by ICP test

Sample	x（Ni）/%	x（Co）/%	x（Mn）/%	x（Mg）/%
NCMMg?0	90.26	4.75	4.99	0
NCMMg?1	89.53	4.54	4.87	1.06
NCMMg?3	87.51	4.53	4.93	3.03
NCMMg?5	86.20	4.46	4.50	4.84
NCMMg?7	84.24	4.51	4.64	6.61

Fig.4 （A） The initial charge and discharge curves of NCMMg-0， NCMMg-1， NCMMg-3， NCMMg-5 and NCMMg-7 samples at 2.8~4.3 V and 0.1 C；（B） Cycle performance of NCMMg-0 and NCMMg-3 at 1 C；（C） Rate performance of NCMMg-0 and NCMMg-3；（D） Lithium ion diffusion coefficient curve of NCMMg-0 and NCMMg-3 sample during charge and discharge

Fig.5 CV curves of cathode materials NCMMg-0 and NCMMg-3

Fig.6 dQ/dV curves of cathode materials （A） NCMMg-0 and （B） NCMMg-3 corresponding to the cycle curves

Fig.7 EIS spectra of NCMMg-0 and NCMMg-3 samples after （A） 10 cycles and （B） 100 cycles

Table 3 Fitting data for EIS

Sample	R_sfafter 10 cycles/Ω	R_ct after 10 cycles/Ω	R_sf after 100 cycles/Ω	R_ct after 100 cycles/Ω
NCMMg?0	21.8	153.9	61.5	374.7
NCMMg?3	18.1	43.8	52.4	85.4

Fig.8 Ni2p2/3 XPS spectra of （A） NCMMg-0 and （B） NCMMg-3 samples after cycling

Fig.9 XRD spectra of NCMMg-0 and NCMMg-3 electrodes after cycling

Fig.10 （A） Low resolution TEM image and （B） high resolution TEM image of NCMMg-0 sample particles after cycling， high resolution TEM image of （C） fresh NCMMg-3 and （D） cycled NCMMg-3

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Synthesis and Properties of Mg‑Doped Ni‑Rich Ternary Cathode Material LiNi_0.90Co_0.05Mn_0.05O₂

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