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

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

doi:10.26434/chemrxiv-2024-hrb24

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

Nickil Shah
, Galo Paez Fajardo (Lead / Corresponding author)
, Hrishit Banerjee
, Gaurav Pandey
, Ashok Menon
, Muhammad Ans
, Veronika Majherova
, Gerard Bree
, Satish Bolloju
, David Grinter
, Pilar Ferrer
, Pardeep Thakur
, Tien-Lin Lee
, Melanie Loveridge
, Andrew J. Morris
, Clare Grey
, Louis Piper

Physics

Research output: Working paper/Preprint › Working paper

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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 rock-salt 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 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
Publisher	ChemRxiv
Number of pages	10
DOIs	https://doi.org/10.26434/chemrxiv-2024-hrb24
Publication status	Published - 17 Dec 2024

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10.26434/chemrxiv-2024-hrb24Licence: CC BY-NC

Pre-printSubmitted manuscript, 1.31 MBLicence: CC BY-NC

Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes
Shah, N. A., Fajardo, G. J. P. (Lead / Corresponding author), 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. (Lead / Corresponding author), 17 Feb 2025, In: ACS Energy Letters. 10, 3, p. 1313-1320 8 p.
Research output: Contribution to journal › Letter › peer-review

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Shah, N., Fajardo, G. P., Banerjee, H., Pandey, G., Menon, A., Ans, M., Majherova, V., Bree, G., Bolloju, S., Grinter, D., Ferrer, P., Thakur, P., Lee, T.-L., Loveridge, M., Morris, A. J., Grey, C., & Piper, L. (2024). Nature of the oxygen loss induced rocksalt layer and its impact on capacity fade in Ni-rich layered oxide cathodes. ChemRxiv. https://doi.org/10.26434/chemrxiv-2024-hrb24

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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 (\textasciitilde{}4.3 V vs. Li+/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rock-salt 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 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.",

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AU - Shah, Nickil

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AU - Pandey, Gaurav

AU - Menon, Ashok

AU - Ans, Muhammad

AU - Majherova, Veronika

AU - Bree, Gerard

AU - Bolloju, Satish

AU - Grinter, David

AU - Ferrer, Pilar

AU - Thakur, Pardeep

AU - Lee, Tien-Lin

AU - Loveridge, Melanie

AU - Morris, Andrew J.

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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 rock-salt 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 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 rock-salt 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 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.

U2 - 10.26434/chemrxiv-2024-hrb24

DO - 10.26434/chemrxiv-2024-hrb24

M3 - Working paper

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

PB - ChemRxiv

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

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