Title: Origin of Rapid Delithiation In Secondary Particles Of LiNi _0.8 Co _0.15 Al _0.05 O ₂ and LiNi _y Mn _z Co _{1− y − z} O ₂ Cathodes

Abstract

Abstract Most research on the electrochemical dynamics in materials for high‐energy Li‐ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two‐phase transformation within LiNi _0.8 Co _0.15 Al _0.05 O ₂ . Here, nano‐focused X‐ray probes are used to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X‐ray microdiffraction (‐XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li‐site fraction ( x _Li ) ≈0.9 and ≈0.5 for LiNi _0.8 Co _0.15 Al _0.05 O ₂ . Physics‐based modeling shows that, to reproduce the experimental results, the exchange current density ( i ₀ ) must depend on x _Li , and that i ₀ should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump in i ₀ are crucialmore » to understanding the charge‐storage reaction of Li‐ion battery cathodes.« less

Authors:

Wolfman, Mark  ^[1];

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May, Brian M.  ^[2];

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Goel, Vishwas ^[3]; Du, Sicen  ^[3];

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Yu, Young‐Sang  ^[4];

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Faenza, Nicholas V. ^[5]; Pereira, Nathalie  ^[5];

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Grenier, Antonin ^[6]; Wiaderek, Kamila M.  ^[7];

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Xu, Ruqing  ^[7];

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Wang, Jiajun ^[8]; Chapman, Karena W. ^[6]; Amatucci, Glenn G. ^[5]; Thornton, Katsuyo ^[3]; Cabana, Jordi  ^[2]

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• Search DOE PAGES for ORCID "0000-0002-2353-5986"

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+ Show Author Affiliations

1. Department of Chemistry University of Illinois at Chicago 845 W Taylor St, 4500 SES (MC 111) Chicago IL 60607 USA, Chemical Sciences and Engineering Division Argonne National Laboratory 9700 S Cass Ave Lemont IL 60439 USA, X‐ray Science Division, Advanced Photon Source Argonne National Laboratory 9700 S Cass Ave Lemont IL 60439 USA
2. Department of Chemistry University of Illinois at Chicago 845 W Taylor St, 4500 SES (MC 111) Chicago IL 60607 USA
3. Department of Materials Science and Engineering University of Michigan 2300 Hayward St Ann Arbor MI 48109 USA
4. Advanced Light Source Lawrence Berkeley National Laboratory 6 Cyclotron Rd Berkeley CA 94720 USA, Department of Physics Chungbuk National University Chungdae‐ro 1, Seowon‐Gu Cheongju Chungbuk 28644 South Korea
5. Energy Storage Research Group, Department of Materials Science and Engineering Rutgers, The State University of New Jersey
6. Department of Chemistry Stony Brook University 100 Nicolls Road Stony Brook NY 11794 USA
7. X‐ray Science Division, Advanced Photon Source Argonne National Laboratory 9700 S Cass Ave Lemont IL 60439 USA
8. Harbin Institute of Technology 92 Xida St, Nangang Harbin Heilongjiang China

Publication Date:

Sun Sep 03 00:00:00 EDT 2023

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:

USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

OSTI Identifier:

1998007

Alternate Identifier(s):

OSTI ID: 1998009; OSTI ID: 2281209

Grant/Contract Number:  

AC02-05CH11231; ERCAP0017801; AC02-06CH11357; AC02-76SF00515; SC0012583; ACI-1053575

Resource Type:

Published Article

Journal Name:

Advanced Energy Materials

Additional Journal Information:

Journal Name: Advanced Energy Materials Journal Volume: 13 Journal Issue: 37; Journal ID: ISSN 1614-6832

Publisher:

Wiley Blackwell (John Wiley & Sons)

Country of Publication:

Germany

Language:

English

Subject:

25 ENERGY STORAGE