First-Principles Study of the Effects of Mg Doping on the Structural and Lithium Deintercalation Properties of Ternary Cathode Material NCM811

doi:10.16553/j.cnki.issn1000-985x.2025.0228

Abstract

Abstract: High-nickel layered ternary oxide LiNi_0.8Co_0.1Mn_0.1O₂ （NCM811） is a promising cathode material for lithium-ion batteries owing to its high specific capacity， high energy density， and cost-effectiveness. In this study， the first-principles calculations were employed to investigate the effects of Mg doping on the structural properties and lithium deintercalation properties of NCM811. The results indicate that Mg preferentially substitutes at Ni sites in NCM811. It shortens the Ni—O bond and increases its bond energy， thereby strengthening oxygen binding， effectively reducing oxygen release， and improving the structural stability of NCM811. Mg doping induces the oxidation of Ni²⁺ to Ni³⁺ in NCM811. During delithiation， both Ni²⁺ and Ni³⁺ serve as redox-active centers， ultimately oxidizing to Ni⁴⁺. Upon complete delithiation， the volume contraction of the Mg@NCM811 is smaller than that of pristine NCM811， indicating that Mg doping can suppress the lattice distortion and improve the structural stability of NCM811 during charge/discharge cycles.

Key words: NCM811; ternary cathode material; Mg doping; first-principles calculation; structural property; lithium deintercalation property

CLC Number:

TB34

MEI Zuyue, MA Mingde, MA Xiaojun, SHI Zhe, CAO Zhijie, MA Ling. First-Principles Study of the Effects of Mg Doping on the Structural and Lithium Deintercalation Properties of Ternary Cathode Material NCM811[J]. Journal of Synthetic Crystals, 2026, 55(5): 791-800.

Figures/Tables 10

References 40

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Computational model	Cell parameter			Cell volume/Å³	Volume change/%
Computational model	a/Å	b/Å	c/Å	Cell volume/Å³	Volume change/%
NCM811^cal	5.71	5.71	14.06	397.70	2.07
NCM811^exp［34］	5.75	5.75	14.20	406.11
Mg doping	5.70	5.79	13.81	396.95	0.19

Computational model	Cell parameter			Cell volume/Å³	Volume change/%
Computational model	a/Å	b/Å	c/Å	Cell volume/Å³	Volume change/%
NCM811^cal	5.71	5.71	14.06	397.70	2.07
NCM811^exp［34］	5.75	5.75	14.20	406.11
Mg doping	5.70	5.79	13.81	396.95	0.19

Doping site	E_f/eV	Doping site	E_f/eV	Doping site	E_f/eV
Ni1	0.37	Ni5	1.03	Ni9	1.63
Ni2	1.03	Ni6	0.95	Ni10	0.52
Ni3	0.42	Ni7	0.06	Co	0.20
Ni4	0.80	Ni8	0.16	Mn	0.45

Doping site	E_f/eV	Doping site	E_f/eV	Doping site	E_f/eV
Ni1	0.37	Ni5	1.03	Ni9	1.63
Ni2	1.03	Ni6	0.95	Ni10	0.52
Ni3	0.42	Ni7	0.06	Co	0.20
Ni4	0.80	Ni8	0.16	Mn	0.45

NCM811				Mg@NCM811
TM—O	Peak position（X）	Peak height（Y）	FWHM	TM—O	Peak position（X）	Peak height（Y）	FWHM
Li—O	2.05	5.41	0.32	Li—O	2.05	5.47	0.32
Ni—O	1.90	9.00	0.23	Ni—O	1.85	9.64	0.17
Co—O	1.90	19.59	0.10	Co—O	1.90	17.62	0.11
Mn—O	1.90	17.25	0.12	Mn—O	1.90	16.96	0.12
				Mg—O	2.00	13.25	0.14