Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries

Chen, Ke; Barai, Pallab; Kahvecioglu, Ozgenur; Wu, Lijun; Pupek, Krzysztof Z.; Ge, Mingyuan; Ma, Lu; Ehrlich, Steven N.; Zhong, Hui; Zhu, Yimei; Srinivasan, Venkat; Bai, Jianming; Wang, Feng

doi:10.1038/s41467-023-44583-3

Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries

Journal Article · Wed Jan 10 00:00:00 EST 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-023-44583-3· OSTI ID:2280727

; Barai, Pallab; ; ; Pupek, Krzysztof Z.; ; Ma, Lu; Ehrlich, Steven N.; Zhong, Hui; ; Srinivasan, Venkat; ;

Abstract

Lithium-ion batteries play a crucial role in decarbonizing transportation and power grids, but their reliance on high-cost, earth-scarce cobalt in the commonly employed high-energy layered Li(NiMnCo)O ₂ cathodes raises supply-chain and sustainability concerns. Despite numerous attempts to address this challenge, eliminating Co from Li(NiMnCo)O ₂ remains elusive, as doing so detrimentally affects its layering and cycling stability. Here, we report on the rational stoichiometry control in synthesizing Li-deficient composite-structured LiNi _0.95 Mn _0.05 O ₂ , comprising intergrown layered and rocksalt phases, which outperforms traditional layered counterparts. Through multiscale-correlated experimental characterization and computational modeling on the calcination process, we unveil the role of Li-deficiency in suppressing the rocksalt-to-layered phase transformation and crystal growth, leading to small-sized composites with the desired low anisotropic lattice expansion/contraction during charging and discharging. As a consequence, Li-deficient LiNi _0.95 Mn _0.05 O ₂ delivers 90% first-cycle Coulombic efficiency, 90% capacity retention, and close-to-zero voltage fade for 100 deep cycles, showing its potential as a Co-free cathode for sustainable Li-ion batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; 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). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2280727

Alternate ID(s):: OSTI ID: 2310275
OSTI ID: 2441297

Report Number(s):: BNL--225299-2024-JAAM; 430; PII: 44583

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries

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