Strain Mechanism Study on Li-rich Layered Cathode Materials Li-Ni-Mn-O for Li-ion Batteries

doi:10.6023/A24110356

Abstract

Lithium-rich layered oxides (LLOs) has attracted the attention of scientists due to its theoretical specific capacity exceeding 250 mAh•g⁻¹. It is considered the most promising new generation of lithium-ion battery cathode materials. However, the aggregation of Li₂MnO₃ domains and the release of lattice oxygen in LLOs can lead to severe capacity/voltage degradation, hindering their commercial applications. This work adopts a manganese-based lithium-rich layered Li_1.17Ni_0.165Co_0.165Mn_0.5O₂ (Li-Ni-Co-Mn-O) model with C2/m symmetry. Select a 2×2×1 supercell with a total of 96 atoms, namely Li₂₈Ni₄Co₄Mn₁₂O₄₈. Construct two systems, one with Co permeation into Li₂MnO₃ domain (LNCMO-P) and the other without (LNCMO-nP), to investigate the effect of Co permeation on the redox process and delithiation structure stability of Li₂MnO₃ domain and O. The spin-polarized generalized gradient approximation (GGA) method with PBE (Perdew Burke Ernzerhof) exchange-correlation function is adopted, and the projected augmented wave (PAW) potential function is selected to describe the interaction between ions and electrons to complete all calculations. The research results indicate that by regulating the concentration of oxygen vacancies, Co can penetrate Li₂MnO₃ domains. The permeation of Co alleviates the stress distortion between Li₂MnO₃ and LiTMO₂ phases and suppresses the lattice strain caused by uneven electrochemical activity and structural evolution. The study on the geometry and electronic structure of the Li_1.17Ni_0.165Co_0.165Mn_0.5O₂ system found that Co-Ni aggregation caused the appearance of high-spin Co electronic states, which alleviated the volume expansion caused by charging. The permeation of Co activates more interfacial oxygen, and oxygen at the interface participates in charge compensation and disperses oxygen oxidation, thereby sharing the oxidation pressure of oxygen in the Li-O-Li configuration, which is beneficial for suppressing the release of lattice oxygen and improving the problem of irreversible oxygen evolution caused by lattice oxygen reactions. This study provides a theoretical basis for designing lithium-rich cathode materials with high-performance structural stability.

Key words: lithium-rich layered oxides, Li₂MnO₃ domain, Co permeation, stress, first-principles calculation

Cite this article

Jihong Liu, Jiapeng Zhu, Xu Zhang, Jiyang Zhang, Chaoyang Huang, Guixiao Jia, Shengli An. Strain Mechanism Study on Li-rich Layered Cathode Materials Li-Ni-Mn-O for Li-ion Batteries[J]. Acta Chimica Sinica, 2025, 83(2): 101-109.

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Fig. & Tab. 4

Figure 1. Structural models of LNCMO-P (a) and LNCMO-nP (b); Various O center coordination configurations and their proportion of the LNCMO-P and LNCMO-nP systems (c); Energy difference between LNCMO-P and LNCMO-nP systems and the proportion of O center coordination configurations with ΔZ=0 as the oxygen vacancy concentration CVO (d)

Figure 2. Delithiation structures of LNCMO-P (a) and LNCMO-nP (b); Changes of lattice parameters and volumes of LNCMO-P (c) and LNCMO-nP (d) as delithiation of Li+ ions

Figure 3. Variations of Mn—O bond length in LNCMO-P (a, d) and LNCMO-nP systems (b, c) as the delithiation of Li+ ions; Schematic diagram of interlayer spacing difference and lattice strain of LiTMO2 and Li2MnO3 phase TMO2 (e)

Figure 4. The schematic diagram of the average delithiation voltage Vave and delithiation position of LNCMO-P and LNCMO-nP systems in Li2MnO3 at the purple coverage area (a); Oxygen vacancy formation enthalpy ΔHO (b); Delithiation energy difference ΔE between two systems (c); O Bader charge and charge density (d); The O-Bader charges of Li2MnO3 phase in LNCMO-P and LNCMO-nP systems (e); Changes in magnetic moments of Co and Ni (f); The spin structure change of Co before and after the valence change of Ni2+ ions (g); Schematic diagram of Co—O bond length changes in low spin cobalt (LS-Co) and high spin cobalt (HS-Co) (h)

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锂离子电池富锂层状正极材料Li-Ni-Mn-O应变机理研究