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 (Lead / Corresponding author), 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 (Lead / Corresponding author)

Physics

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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, 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.

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

Keywords

Electrochemical cells
Electrodes
Layers
Oxides
Surface chemistry

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10.1021/acsenergylett.5c00324Licence: CC BY

Final Published VersionFinal published version, 5.75 MBLicence: CC BY

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Shah, N. A., Fajardo, G. J. P., 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, 1313-1320. https://doi.org/10.1021/acsenergylett.5c00324

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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.",

keywords = "Electrochemical cells, Electrodes, Layers, Oxides, Surface chemistry",

author = "Shah, {Nickil A.} and Fajardo, {Galo J. P{\'a}ez} 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 Tien-Lin Lee and Loveridge, {Melanie J.} and Morris, {Andrew J.} and Grey, {Clare P.} and Piper, {Louis F. J.}",

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year = "2025",

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day = "17",

doi = "10.1021/acsenergylett.5c00324",

language = "English",

volume = "10",

pages = "1313--1320",

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Shah, NA, Fajardo, GJP, Banerjee, H, Pandey, GC, Menon, AS, Ans, M, Majherova, V, Bree, G, Bolloju, S, Grinter, DC, Ferrer, P, Thakur, PK, Lee, T-L, 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, pp. 1313-1320. https://doi.org/10.1021/acsenergylett.5c00324

TY - JOUR

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 - Fajardo, Galo J. Páez

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 - 2025/2/17

Y1 - 2025/2/17

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.

KW - Electrochemical cells

KW - Electrodes

KW - Layers

KW - Oxides

KW - Surface chemistry

UR - http://www.scopus.com/inward/record.url?scp=85217971047&partnerID=8YFLogxK

U2 - 10.1021/acsenergylett.5c00324

DO - 10.1021/acsenergylett.5c00324

M3 - Letter

VL - 10

SP - 1313

EP - 1320

JO - ACS Energy Letters

JF - ACS Energy Letters

ER -

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

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Keywords

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Nature of the oxygen loss induced rocksalt layer and its impact on capacity fade in Ni-rich layered oxide cathodes

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