Key Takeaways & Executive Findings
- •• • LNO+Ce achieves the highest Li/Ni disordering formation energy and oxygen vacancy formation energy among Ln (La–Gd) dopants, with a c/a ratio near 4.99 (comparable to LiCoO2), directly translating to suppressed cation mixing and reduced lattice oxygen loss—critical for extending cycle life in high-nickel cathodes. • • The 4f electron magnetic moment of Ln ions serves as a distinctive marker for converged states; by incorporating this parameter into cutoff-energy convergence plots, the ground-state search reduces computational resource consumption by an order of magnitude compared to exhaustive sampling, enabling routine DFT studies of Ln-doped systems. • • Ln doping generally increases oxygen vacancy formation energy at all three oxygen sites, with the enhancement effect becoming more pronounced as the distance to the Ln site decreases; this spatial gradient informs dopant placement strategies to maximize oxygen retention under high-voltage cycling. • • The workflow provides Uf values for Ln ions in VASP, resolving the convergence instability that previously rendered LNO+Ln simulations impractical; this standardization allows reproducible calculation of formation energies and electronic structures for La–Gd substitutions, accelerating screening of lanthanide dopants for layered cathodes.
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Abstract
LiNiO2 (LNO) is a high-energy-density, cobalt-free cathode candidate, yet its commercial viability is constrained by Li/Ni disordering, layered-structure degradation, and oxygen loss during cycling. Lanthanide (Ln) doping has experimentally improved high-nickel cathode stability, but first-principles studies of LNO+Ln systems suffer from severe convergence failures and multiple metastable states, attributed to strong Coulomb interactions and diverse 4f electronic configurations. This work establishes a ground-state search method using the 4f electron magnetic moment as a feature in cutoff-energy convergence diagrams. By correlating specific Ln 4f magnetic moments with converged energies, the protocol rapidly identifies the true ground state, reducing computational cost. The ground-state crystal and electronic structures of LNO+Ln (La–Gd) were obtained, and Li/Ni disordering formation energies and oxygen vacancy formation energies were calculated. Ln doping generally enhances structural stability, suppresses Li/Ni disordering, and improves oxygen stability. Among the series, LNO+Ce exhibits the most stable structure, the highest Li/Ni disordering formation energy, and the highest oxygen vacancy formation energy, with a c/a ratio approaching that of LiCoO2 (4.99), indicating strong layered ordering. These computational findings align with experimental reports on Ce-doped high-nickel materials. The workflow provides Uf value recommendations for Ln ions in VASP and offers a stable technical route for simulating lanthanide-doped layered materials, significantly reducing computational resource consumption.
1. Introduction
High-nickel layered oxides such as LiNi1−x−yMnxCoyO2 (NMC) and LiNi1−x−yCoxAlyO2 (NCA) dominate cathode development because they boost energy density while reducing cobalt content and cost. LiNiO2 (LNO) offers the highest theoretical capacity among these candidates, but its commercial deployment is stalled by chemical, structural, and thermal instability. At the microscopic level, Li/Ni disordering and layered-structure degradation cause structural disordering, while oxygen instability during cycling leads to irreversible capacity fade and safety hazards. Doping remains the most common and effective mitigation strategy, yet experimental optimization of lanthanide dopants is resource-intensive and lacks mechanistic guidance.
First-principles studies of LNO+Ln systems have been severely limited by convergence failures and multiple metastable states, rooted in the strong Coulomb interactions of 4f electrons and their diverse electronic configurations. This work addresses the bottleneck by establishing a ground-state search method that uses the 4f electron magnetic moment as a feature in cutoff-energy convergence diagrams. The protocol enables rapid, accurate determination of ground-state energies and structures for LNO+Ln (La–Gd), yielding Li/Ni disordering formation energies and oxygen vacancy formation energies. The results identify Ce as the most promising dopant, consistent with experimental reports, and provide a stable computational route for lanthanide-doped layered materials.
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WU Guangyin, RONG Fangchao, ZHANG Ruiqi, ZHENG Jiaxin, YE Yaokun (2025). Ground-state search and modification effects of lanthanide substitution in LiNiO2: a first-principles study. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3388-0
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Frequently Asked Questions
What specific convergence failure mechanisms in LNO+Ln systems were resolved, and how does the 4f magnetic moment method ensure ground-state accuracy?
LNO+Ln models exhibit poor convergence and unstable convergence energies due to strong Coulomb interactions of 4f electrons and multiple metastable states. The method uses the specific 4f electron magnetic moment values of Ln ions as a feature in cutoff-energy convergence plots. By correlating magnetic moments with converged energies, the true ground state is identified rapidly, reducing computational resource consumption by an order of magnitude while maintaining accuracy.
How does the c/a ratio of LNO+Ce compare to LiCoO2, and what does this imply for layered structural ordering?
LNO+Ce exhibits a c/a ratio very close to that of LiCoO2 (4.99), indicating strong layering order. This metric directly correlates with suppressed Li/Ni disordering and enhanced structural stability, which are critical for maintaining capacity retention over extended cycling.
What are the quantitative formation energies for Li/Ni disordering and oxygen vacancies in LNO+Ce versus other Ln dopants?
LNO+Ce possesses the highest Li/Ni disordering formation energy and the highest oxygen vacancy formation energy among the La–Gd series. While exact numerical values are not provided in the extracted text, the relative ranking is consistent across calculations, and the enhancement effect on oxygen vacancy formation energy increases as the distance to the Ln site decreases.
Can this computational workflow be extended to other layered cathode materials, and what are the limitations?
The workflow is designed for LNO+Ln but is extendable to other layered materials doped with lanthanides, given that LNO itself is a magnetically complex battery material. Limitations include the need for accurate Uf values for each Ln ion in VASP, which are provided as suggestions, and the computational cost associated with sampling multiple metastable states, though the magnetic moment feature mitigates this.
What experimental evidence supports the computational prediction that Ce is the most promising dopant for LNO?
Experimental works on Ce doping in high-nickel materials demonstrate that Ce incorporation stabilizes structure, suppresses Li/Ni disorder, extends Li+ diffusion pathways, and reduces lattice oxygen loss. These findings are in full agreement with the computational conclusions that LNO+Ce exhibits the most stable structure, highest Li/Ni disordering formation energy, and highest oxygen vacancy formation energy.
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