Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes

Nickil A. Shah; Galo J. Páez Fajardo; Hrishit Banerjee; Gaurav C. Pandey; Ashok S. Menon; Muhammad Ans; Veronika Majherova; Gerard Bree; Satish Bolloju; David C. Grinter; Pilar Ferrer; Pardeep K. Thakur; Tien Lin Lee; Melanie J. Loveridge; Andrew J. Morris; Clare P. Grey; Louis F.J. Piper

doi:10.1021/acsenergylett.5c00324

Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes

Nickil A. Shah
, Galo J. Páez Fajardo^*
, Hrishit Banerjee
, Gaurav C. Pandey
, Ashok S. Menon
, Muhammad Ans
, Veronika Majherova
, Gerard Bree
, Satish Bolloju
, David C. Grinter
, Pilar Ferrer
, Pardeep K. Thakur
, Tien Lin Lee
, Melanie J. Loveridge
, Andrew J. Morris
, Clare P. Grey
, Louis F.J. Piper^*

^*Corresponding author for this work

Metallurgy and Materials

Research output: Contribution to journal › Letter › peer-review

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Abstract

In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li⁺/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiO_x, and/or Li_yNi_zO) that have different Li⁺ transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li⁺ kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and Li_xNi_1-xO. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.

Original language	English
Pages (from-to)	1313-1320
Number of pages	8
Journal	ACS Energy Letters
Volume	10
Issue number	3
Early online date	17 Feb 2025
DOIs	https://doi.org/10.1021/acsenergylett.5c00324
Publication status	Published - 14 Mar 2025

Bibliographical note

Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

ASJC Scopus subject areas

Chemistry (miscellaneous)
Renewable Energy, Sustainability and the Environment
Fuel Technology
Energy Engineering and Power Technology
Materials Chemistry

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Shah, N. A., Páez Fajardo, G. J., Banerjee, H., Pandey, G. C., Menon, A. S., Ans, M., Majherova, V., Bree, G., Bolloju, S., Grinter, D. C., Ferrer, P., Thakur, P. K., Lee, T. L., Loveridge, M. J., Morris, A. J., Grey, C. P., & Piper, L. F. J. (2025). Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes. ACS Energy Letters, 10(3), 1313-1320. https://doi.org/10.1021/acsenergylett.5c00324

@article{d6ba40550ea14d669027048ad7b3e04b,

title = "Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes",

abstract = "In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li+/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiOx, and/or LiyNizO) that have different Li+ transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li+ kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and LixNi1-xO. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.",

author = "Shah, \{Nickil A.\} and \{P{\'a}ez Fajardo\}, \{Galo J.\} and Hrishit Banerjee and Pandey, \{Gaurav C.\} and Menon, \{Ashok S.\} and Muhammad Ans and Veronika Majherova and Gerard Bree and Satish Bolloju and Grinter, \{David C.\} and Pilar Ferrer and Thakur, \{Pardeep K.\} and Lee, \{Tien Lin\} and Loveridge, \{Melanie J.\} and Morris, \{Andrew J.\} and Grey, \{Clare P.\} and Piper, \{Louis F.J.\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Authors. Published by American Chemical Society.",

year = "2025",

month = mar,

day = "14",

doi = "10.1021/acsenergylett.5c00324",

language = "English",

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Shah, NA, Páez Fajardo, GJ, Banerjee, H, Pandey, GC, Menon, AS, Ans, M, Majherova, V, Bree, G, Bolloju, S, Grinter, DC, Ferrer, P, Thakur, PK, Lee, TL, Loveridge, MJ, Morris, AJ, Grey, CP & Piper, LFJ 2025, 'Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes', ACS Energy Letters, vol. 10, no. 3, pp. 1313-1320. https://doi.org/10.1021/acsenergylett.5c00324

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T1 - Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes

AU - Shah, Nickil A.

AU - Páez Fajardo, Galo J.

AU - Banerjee, Hrishit

AU - Pandey, Gaurav C.

AU - Menon, Ashok S.

AU - Ans, Muhammad

AU - Majherova, Veronika

AU - Bree, Gerard

AU - Bolloju, Satish

AU - Grinter, David C.

AU - Ferrer, Pilar

AU - Thakur, Pardeep K.

AU - Lee, Tien Lin

AU - Loveridge, Melanie J.

AU - Morris, Andrew J.

AU - Grey, Clare P.

AU - Piper, Louis F.J.

PY - 2025/3/14

Y1 - 2025/3/14

N2 - In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li+/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiOx, and/or LiyNizO) that have different Li+ transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li+ kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and LixNi1-xO. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.

AB - In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li+/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiOx, and/or LiyNizO) that have different Li+ transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li+ kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and LixNi1-xO. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.

UR - https://www.scopus.com/pages/publications/85217971047

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DO - 10.1021/acsenergylett.5c00324

M3 - Letter

AN - SCOPUS:85217971047

SN - 2380-8195

VL - 10

SP - 1313

EP - 1320

JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 3

ER -

Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes

Abstract

Bibliographical note

UN SDGs

ASJC Scopus subject areas

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