by Jesus Díaz-Sánchez, Ingeborg S. Ellingsen, Elena Salagre, Jesús Sánchez-Prieto, Noelia Maldonado, Arturo Galindo, Carmen Morant, Enrique Vasco, Gastón Garcia, Daniel Rettenwander, Juan Rubio-Zuazo, Enrique G. Michel and Celia Polop
Abstract:
Understanding charge compensation mechanisms in nickel-rich lithium nickel–manganese–cobalt alloy oxide (NMC) cathodes is crucial for optimizing their electrochemical performance. This study employs complementary spectroscopic techniques with varying probing depths, including X-ray absorption near-edge structure spectroscopy, hard X-ray photoemission spectroscopy, X-ray photoelectron spectroscopy, and ion beam analysis, to investigate the correlation between transition metal oxidation states and Li depth profile in NMC811. This approach reveals different charge compensation mechanisms depending on the local Li content, which exhibits near-surface gradients. The results show that Ni oxidation is the main charge compensation mechanism for moderate delithiations at a Li stoichiometry x textgreater 0.35. When the Li content drops below the threshold x = 0.3, which occurs near the surface for high state of charge (SOC), compensation by Ni/Li mixing prevails. Meanwhile, the Li-depleted surface (with x ≪ 0.3) shows evidence of transformation into electrochemically inactive Li-free cubic phases. The voltage window used to cycle the NMC811 prevents the bulk Li content from falling below x = 0.35, so the different charge compensation mechanisms coexist for high SOCs, allowing to compare between their kinetics. This study contributes to a comprehensive understanding of the electrochemical behavior of nickel-rich NMCs, aiding the development of high-energy Li-ion batteries with improved stability.
Reference:
Jesus Díaz-Sánchez, Ingeborg S. Ellingsen, Elena Salagre, Jesús Sánchez-Prieto, Noelia Maldonado, Arturo Galindo, Carmen Morant, Enrique Vasco, Gastón Garcia, Daniel Rettenwander, Juan Rubio-Zuazo, Enrique G. Michel and Celia Polop, “Charge Compensation Mechanisms in Ni-Rich NMC Cathodes”, Batteries & Supercaps, vol. n/a, no. n/a, pp. 2500167.
Bibtex Entry:
@article{diaz-sanchez_charge_2025,
title = {Charge {Compensation} {Mechanisms} in {Ni}-{Rich} {NMC} {Cathodes}},
volume = {n/a},
copyright = {© 2025 The Author(s). Batteries & Supercaps published by Wiley-VCH GmbH},
issn = {2566-6223},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/batt.202500167},
doi = {10.1002/batt.202500167},
abstract = {Understanding charge compensation mechanisms in nickel-rich lithium nickel–manganese–cobalt alloy oxide (NMC) cathodes is crucial for optimizing their electrochemical performance. This study employs complementary spectroscopic techniques with varying probing depths, including X-ray absorption near-edge structure spectroscopy, hard X-ray photoemission spectroscopy, X-ray photoelectron spectroscopy, and ion beam analysis, to investigate the correlation between transition metal oxidation states and Li depth profile in NMC811. This approach reveals different charge compensation mechanisms depending on the local Li content, which exhibits near-surface gradients. The results show that Ni oxidation is the main charge compensation mechanism for moderate delithiations at a Li stoichiometry x {textgreater} 0.35. When the Li content drops below the threshold x = 0.3, which occurs near the surface for high state of charge (SOC), compensation by Ni/Li mixing prevails. Meanwhile, the Li-depleted surface (with x ≪ 0.3) shows evidence of transformation into electrochemically inactive Li-free cubic phases. The voltage window used to cycle the NMC811 prevents the bulk Li content from falling below x = 0.35, so the different charge compensation mechanisms coexist for high SOCs, allowing to compare between their kinetics. This study contributes to a comprehensive understanding of the electrochemical behavior of nickel-rich NMCs, aiding the development of high-energy Li-ion batteries with improved stability.},
language = {en},
number = {n/a},
urldate = {2025-08-01},
journal = {Batteries & Supercaps},
author = {Díaz-Sánchez, Jesus and Ellingsen, Ingeborg S. and Salagre, Elena and Sánchez-Prieto, Jesús and Maldonado, Noelia and Galindo, Arturo and Morant, Carmen and Vasco, Enrique and Garcia, Gastón and Rettenwander, Daniel and Rubio-Zuazo, Juan and Michel, Enrique G. and Polop, Celia},
year = {2025},
keywords = {Li-ion battery, ion beam analysis, NMC cathodes, photoemission spectroscopy},
pages = {2500167},
file = {Full Text PDF:E:\Usuarios\Administrator\Zotero\storage\HX27CC67\Díaz-Sánchez et al. - Charge Compensation Mechanisms in Ni-Rich NMC Cathodes.pdf:application/pdf;Snapshot:E:\Usuarios\Administrator\Zotero\storage\7NKI4PRH\batt.html:text/html},
}