Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

Xiao, Biwei; Zheng, Yu; Song, Miao; Liu, Xiang; Lee, Gi‐Hyeok; Omenya, Fred; Yang, Xin; Engelhard, Mark H.; Reed, David; Yang, Wanli; Amine, Khalil; Xu, Gui‐Liang; Balbuena, Perla B.; Li, Xiaolin

doi:10.1002/adma.202308380

Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

Journal Article · Wed Jan 10 00:00:00 EST 2024 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202308380· OSTI ID:2281063

Xiao, Biwei ^[1]; Zheng, Yu ^[2]; Song, Miao ^[3]; Liu, Xiang ^[4]; Lee, Gi‐Hyeok ^[5]; Omenya, Fred ^[1]; Yang, Xin ^[1]; Engelhard, Mark H. ^[6]; Reed, David ^[1]; Yang, Wanli ^[7]; Amine, Khalil ^[4]; Xu, Gui‐Liang ^[4]; Balbuena, Perla B. ^[8]; ^[1]

Energy &, Environment Directorate Pacific Northwest National Laboratory Richland WA 99352 USA
Department of Chemical Engineering Texas A&,M University College Station TX 77843‐3122 USA, Department of Chemistry Texas A&,M University College Station TX 77843‐3122 USA
Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland WA 99352 USA
Chemical Sciences and Engineering Division Argonne National Laboratory 9700 South Cass Avenue Lemont IL 60439 USA
Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Department of Materials Science and Engineering Dongguk University Seoul 04620 Republic of Korea
Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory Richland WA 99352 USA
Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Department of Chemical Engineering Texas A&,M University College Station TX 77843‐3122 USA, Department of Chemistry Texas A&,M University College Station TX 77843‐3122 USA, Department of Materials Science and Engineering Texas A&,M University College Station TX 77843‐3122 USA

Abstract

Protonation of oxide cathodes triggers surface transition metal dissolution and accelerates the performance degradation of Li‐ion batteries. While strategies are developed to improve cathode material surface stability, little is known about the effects of protonation on bulk phase transitions in these cathode materials or their sodium‐ion battery counterparts. Here, using NaNiO ₂ in electrolytes with different proton‐generating levels as model systems, a holistic picture of the effect of incorporated protons is presented. Protonation of lattice oxygens stimulate transition metal migration to the alkaline layer and accelerates layered‐rock‐salt phase transition, which leads to bulk structure disintegration and anisotropic surface reconstruction layers formation. A cathode that undergoes severe protonation reactions attains a porous architecture corresponding to its multifold performance fade. This work reveals that interactions between electrolyte and cathode that result in protonation can dominate the structural reversibility/stability of bulk cathodes, and the insight sheds light for the development of future batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: Texas A&M University; USDOE; USDOE Office of Electricity (OE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2281063

Alternate ID(s):: OSTI ID: 2337816
OSTI ID: 2348885
OSTI ID: 2484295
OSTI ID: 2281442

Report Number(s):: PNNL-SA--169982; 2308380

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 13 Vol. 36; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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25 ENERGY STORAGE
layered cathode materials
protonation
rock-salt phase
sodium-ion batteries

Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

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