Theoretical Study on the Structural Stability and Oxygen Ion Oxidation of Al-doped Lithium-ion Battery Layered Cathode Li(Li0.17Ni0.17Al0.04Fe0.13Mn0.49)O2

doi:10.6023/A21040178

Abstract

In lithium-ion battery, lithium rich layered transition metal oxides materials are the next generation of lithium ion cathode materials with high practical specific capacity. The specific capacity and structural stability of cathode materials are two important factors. In order to improve the overall performance of batteries, some strategies such as chemical modifications, surface coating and material composite are used. Among them element doping is an effectively method to improve the electrochemical stability of lithium-rich cathode materials. Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂ (LNAFMO) as a layered cobalt-free cathode material was selected as the research object. Geometrical structures including the lattice parameters, M―O bond length (where M stands for transition metal) and O―O bond length, electronic structures including oxidation processes of transition metal and oxygen ion, oxygen release enthalpies, delithium formation energies, delithium voltage and the effect of doping element Al are investigated by a GGA (generalized gradient approximation)+U (Hubbard U value) method. Calculated results show that Ni²⁺ ions in the LNAFMO system are first oxidized, then Fe³⁺ and finally O^2- during the charging. Oxygen ions with linear Al-O-Li configurations in the LNAFMO system participate in charge compensation besides those with linear Li-O-Li and Fe-O-Li configurations, different from the Li(Li_0.17Ni_0.17Fe_0.17Mn_0.49)O₂ (LNFMO) system without Al doping. The doping of Al can suppress the release of oxygen, improving the structural stability of the system and the cycling performance of the battery. The doping of Al increases the special capacity of LNFMO system (246 mAh•g^-1), in which the contribution of Ni/Fe transition metal and oxygen ions to the capacity is equal. The internal mechanism between the oxidation of transition metals and oxygen ions and the geometrical structures in the system has been revealed from a microscopic perspective. This work would provide a theoretical basis for the design of a low cost, high energy density and high cycle performance lithium-ion battery cathode material.

Key words: lithium-ion battery, lithium-rich cathode material, doping, anionic oxidation, first-principles calculation

Cite this article

Kai Qiu, Mingxia Yan, Shouwang Zhao, Shengli An, Wei Wang, Guixiao Jia. Theoretical Study on the Structural Stability and Oxygen Ion Oxidation of Al-doped Lithium-ion Battery Layered Cathode Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂[J]. Acta Chimica Sinica, 2021, 79(9): 1146-1153.

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Fig. & Tab. 8

Figure 1. The most stable structures of Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system, x=0~24 (a)~(l)

x	a/Å	b/Å	c/Å	β/(°)	d/Å
0	5.04	4.36	5.10	109.19	2.05	—	0	—	—
2	5.02	4.37	5.10	108.79	2.81	0.00	–1.87	–0.73	3.39
4	5.00	4.38	5.10	108.43	2.85	0.01	–3.91	–0.69	3.30
6	5.01	4.36	5.12	108.61	2.89	0.07	–5.36	–0.68	3.60
8	5.02	4.35	5.13	108.35	2.93	0.48	–7.14	–0.66	3.43
10	5.01	4.34	5.17	107.96	3.00	1.23	–7.83	–0.64	3.98
12	5.01	4.34	5.21	108.33	3.06	0.82	–7.77	–0.60	4.36
14	4.99	4.34	5.25	109.71	3.08	0.96	–7.45	–0.56	4.48
16	4.99	4.33	5.28	109.61	3.13	1.34	–7.00	–0.51	4.55
18	4.99	4.33	5.31	110.77	3.18 3.21	1.48	–5.88	–0.46	4.88
20	5.02	4.36	5.36	112.51	3.18 3.21	1.45	–4.50	–0.43	5.02
22	4.99	4.30	5.30	112.20	3.13	–0.65	–5.20	–0.51	3.97
24	5.01	4.30	5.03	110.22	2.98	–1.87	–1.32	–0.38	6.27

Table 1. Unit cell parameters, O―O layer spacing (d), volume change before and after delithiation (ΔV), enthalpy change ΔHLi, twisting energy (Ed) and average delithiation potential (Vave) of the Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system

Figure 2. Variation curves of Ni―O (a), Fe―O (b) and Mn―O (c) bond lengthes and oxygen vacancy formation enthalpy ΔHo (d) as x in the Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system

System	M	E_b/eV
LNAFMO	Fe	1.28	1.29
	Ni	1.26
	Mn	1.30
	Al	1.30
LNFMO	Fe	1.15	1.19
	Ni	1.18
	Mn	1.25

Table 2. Binding energy Eb and average binding energy ${{\overline{E}}_{\text{b}}}$of M―O bonds in LNAFMO and LNFMO systems

Figure 3. Evolution of density of states of Ni (a), Fe (b), four kinds of O (c) and all O (d) as x in the Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system, and Fermi level is set to 0

Figure 4. Density of states for Fe and O in the Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system at x=10 and 12. The solid line shows the energy cutoff for every Li28-xNi4AlFe3Mn12O48 molecule losing two electrons, and the dotted line is the Fermi energy level and set to 0

. The charge densities of the Li28-xNi4AlFe3Mn12O48 (0≤x≤24) system at x=0 (a), 10 (b)和12 (c). The charge density around oxygen is yellow, the red dotted circle represents the removed lithium ions, and the black dotted line ellipse represents the O2p orbital. Two local structures containing oxidized oxygen ions are presented in figure 6c

Figure 6. Crystal structures of monoclinic LNFMO (a) and LNAFMO (b) systems

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Al掺杂的锂离子电池层状正极材料Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂结构稳定性及氧离子氧化的理论研究

Theoretical Study on the Structural Stability and Oxygen Ion Oxidation of Al-doped Lithium-ion Battery Layered Cathode Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂

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Al掺杂的锂离子电池层状正极材料Li(Li0.17Ni0.17Al0.04Fe0.13Mn0.49)O2结构稳定性及氧离子氧化的理论研究