REFERENCES
1. Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 2020, 11, 1550.
2. Chen, H.; Xia, X.; Ma, J. Comprehensive review of Li-rich Mn-based layered oxide cathode materials for lithium-ion batteries: theories, challenges, strategies and perspectives. ChemSusChem 2024, 17, e202401120.
3. Sathiya, M.; Rousse, G.; Ramesha, K.; et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 2013, 12, 827-35.
4. Seo, D. H.; Lee, J.; Urban, A.; Malik, R.; Kang, S.; Ceder, G. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 2016, 8, 692-7.
5. Assat, G.; Tarascon, J. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy. 2018, 3, 373-86.
6. Qiu, B.; Zhou, Y.; Liang, H.; et al. Negative thermal expansion and oxygen-redox electrochemistry. Nature 2025, 640, 941-6.
7. Li, Q.; Ning, D.; Wong, D.; et al. Improving the oxygen redox reversibility of Li-rich battery cathode materials via coulombic repulsive interactions strategy. Nat. Commun. 2022, 13, 1123.
8. Gent, W. E.; Lim, K.; Liang, Y.; et al. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 2017, 8, 2091.
9. Zhang, J.; Wang, Q.; Li, S.; et al. Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide. Nat. Commun. 2020, 11, 6342.
10. Marie, J. J.; House, R. A.; Rees, G. J.; et al. Trapped O2 and the origin of voltage fade in layered Li-rich cathodes. Nat. Mater. 2024, 23, 818-25.
11. Ren, M.; Jiao, S.; Zhao, Y.; et al. Thermal decomposition mechanisms and inherent stability differences between O2- and O3-lithium-rich manganese-based oxide cathodes. Adv. Funct. Mater. 2026, 36, e30009.
12. Lei, Y.; Ni, J.; Hu, Z.; et al. Surface modification of Li‐rich Mn‐based layered oxide cathodes: challenges, materials, methods, and characterization. Adv. Energy. Mater. 2020, 10, 2002506.
13. Kou, P.; Zhang, L.; Zhang, Z.; et al. Oxygen vacancy engineering for high-performance Li-rich manganese cathodes: advances and prospects. Energy. Storage. Mater. 2025, 79, 104321.
14. Qiu, B.; Zhang, M.; Wu, L.; et al. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries. Nat. Commun. 2016, 7, 12108.
15. Zhao, J.; Su, Y.; Dong, J.; et al. Regulating anionic redox reversibility in Li-rich layered cathodes via diffusion-induced entropy-assisted surface engineering. Energy. Storage. Mater. 2024, 70, 103550.
16. Luo, D.; Xie, H.; Tan, F.; et al. Scalable nitrate treatment for constructing integrated surface structures to mitigate capacity fading and voltage decay of Li-rich layered oxides. Angew. Chem. Int. Ed. Engl. 2022, 61, e202203698.
17. Wang, F.; Zuo, P.; Xue, Z.; Liu, Y.; Wang, C.; Chen, G. Fluorination effect on lithium- and manganese-rich layered oxide cathodes. ACS. Energy. Lett. 2024, 9, 1249-60.
18. Jang, H. Y.; Eum, D.; Cho, J.; et al. Structurally robust lithium-rich layered oxides for high-energy and long-lasting cathodes. Nat. Commun. 2024, 15, 1288.
19. Li, B.; Zhuo, Z.; Zhang, L.; et al. Decoupling the roles of Ni and Co in anionic redox activity of Li-rich NMC cathodes. Nat. Mater. 2023, 22, 1370-9.
20. Ravel, B.; Newville, M. Athena, Artemis, Hephaestus: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron. Radiat. 2005, 12, 537-41.
21. Bhamidi, V.; Kenis, P. J. A.; Zukoski, C. F. Probability of nucleation in a metastable zone: induction supersaturation and implications. Crystal. Growth. Design. 2017, 17, 1132-45.
22. Liu, X. Y. Generic mechanism of heterogeneous nucleation and molecular interfacial effects. In: Advances in crystal growth research. Elsevier; 2001. pp 42-61.
23. Lamer, V. K.; Dinegar, R. H. Theory, production and mechanism of formation of monodispersed hydrosols. J. Am. Chem. Soc. 1950, 72, 4847-54.
24. Liu, X. Y. A new kinetic model for three-dimensional heterogeneous nucleation. J. Chem. Phys. 1999, 111, 1628-35.
26. Yu, H.; So, Y. G.; Kuwabara, A.; et al. Crystalline grain interior configuration affects lithium migration kinetics in Li-rich layered oxide. Nano. Lett. 2016, 16, 2907-15.
27. Yin, C.; Wei, Z.; Zhang, M.; et al. Structural insights into composition design of Li-rich layered cathode materials for high-energy rechargeable battery. Mater. Today. 2021, 51, 15-26.
28. Kang, K.; Ceder, G. Factors that affect Li mobility in layered lithium transition metal oxides. Phys. Rev. B. 2006, 74.
29. Lanz, P.; Villevieille, C.; Novák, P. Ex situ and in situ Raman microscopic investigation of the differences between stoichiometric LiMO2 and high-energy xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn). Electrochimica. Acta. 2014, 130, 206-12.
30. Zhu, Z.; Yu, D.; Yang, Y.; et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. Nat. Energy. 2019, 4, 1049-58.
31. Julien, C.; Massot, M. Lattice vibrations of materials for lithium rechargeable batteries I. Lithium manganese oxide spinel. Mat. Sci. Eng. B-Adv. 2003, 97, 217-30.
32. Wu, T.; Liu, X.; Zhang, X.; et al. Full concentration gradient-tailored Li-rich layered oxides for high-energy lithium-ion batteries. Adv. Mater. 2021, 33, e2001358.
33. Jarvis, K.; Wang, C.; Varela, M.; Unocic, R. R.; Manthiram, A.; Ferreira, P. J. Surface reconstruction in Li-Rich layered oxides of Li-ion batteries. Chem. Mater. 2017, 29, 7668-74.
34. Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.; et al. Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: methodology, insights and novel approaches. Mat. Sci. Eng. B-Adv. 2015, 192, 3-25.
35. Zheng, J.; Xu, P.; Gu, M.; et al. Structural and chemical evolution of Li- and Mn-rich layered cathode material. Chem. Mater. 2015, 27, 1381-90.
36. Bak, S.; Nam, K.; Chang, W.; et al. Correlating structural changes and gas evolution during the thermal decomposition of charged LixNi0.8Co0.15Al0.05O2 cathode materials. Chem. Mater. 2013, 25, 337-51.
37. Wang, L.; Maxisch, T.; Ceder, G. A first-principles approach to studying the thermal stability of oxide cathode materials. Chem. Mater. 2007, 19, 543-52.
38. Armstrong, A. R.; Holzapfel, M.; Novák, P.; et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. J. Am. Chem. Soc. 2006, 128, 8694-8.
39. Zhou, Y.; Cui, H.; Qiu, B.; et al. Sufficient oxygen redox activation against voltage decay in Li-rich layered oxide cathode materials. ACS. Mater. Lett. 2021, 3, 433-41.
40. Kuball, M.; Hayes, J. M.; Suski, T.; et al. High-pressure high-temperature annealing of ion-implanted GaN films monitored by visible and ultraviolet micro-Raman scattering. J. Appl. Phys. 2000, 87, 2736-41.
41. Baddour-Hadjean, R.; Pereira-Ramos, J. P. Raman microspectrometry applied to the study of electrode materials for lithium batteries. Chem. Rev. 2010, 110, 1278-319.
42. Flores, E.; Novák, P.; Berg, E. J. In situ and operando Raman spectroscopy of layered transition metal oxides for Li-ion battery cathodes. Front. Energy. Res. 2018, 6, 82.
43. Yu, X.; Lyu, Y.; Gu, L.; et al. Understanding the rate capability of high-energy-density Li‐rich layered Li1.2Ni0.15Co0.1Mn0.55O2 cathode materials. Adv. Energy. Mater. 2014, 4, 1300950.



