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Title: Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries

Abstract

The electrochemical kinetics of battery electrodes at the single-particle scale are measured as a function of state-of-charge, and interpreted with the aid of concurrent transmission X-ray microscopy (TXM) of the evolving particle microstructure. An electrochemical cell operating with near-picoampere current resolution is used to characterize single secondary particles of two widely-used cathode compounds, NMC333 and NCA. Interfacial charge transfer kinetics are found to vary by two orders of magnitude with state-of-charge (SOC) in both materials, but the origin of the SOC dependence differs greatly. NCA behavior is dominated by electrochemically-induced microfracture, although thin binder coatings significantly ameliorate mechanical degradation, while NMC333 demonstrates strongly increasing interfacial reaction rates with SOC for chemical reasons. Micro-PITT is used to separate interfacial and bulk transport rates, and show that for commercially relevant particle sizes, interfacial transport is rate-limiting at low SOC, while mixed-control dominates at higher SOC. These results provide mechanistic insight into the mesoscale kinetics of ion intercalation compounds, which can guide the development of high performance rechargeable batteries.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [2];  [2]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]
  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, USA, Department of Materials Science and Engineering
  2. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, USA
  3. Department of Chemistry, University of Illinois at Chicago, Chicago, USA
  4. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, USA
Publication Date:
Research Org.:
State Univ. of New York (SUNY), Binghamton, NY (United States). Energy Frontier Research Center (EFRC) NorthEast Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1426310
Alternate Identifier(s):
OSTI ID: 1470238
Grant/Contract Number:  
SC0012583; AC02-76SF00515; AC02-06CH11357; SC0001294
Resource Type:
Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science Journal Volume: 11 Journal Issue: 4; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Tsai, Ping-Chun, Wen, Bohua, Wolfman, Mark, Choe, Min-Ju, Pan, Menghsuan Sam, Su, Liang, Thornton, Katsuyo, Cabana, Jordi, and Chiang, Yet-Ming. Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries. United Kingdom: N. p., 2018. Web. doi:10.1039/C8EE00001H.
Tsai, Ping-Chun, Wen, Bohua, Wolfman, Mark, Choe, Min-Ju, Pan, Menghsuan Sam, Su, Liang, Thornton, Katsuyo, Cabana, Jordi, & Chiang, Yet-Ming. Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries. United Kingdom. doi:10.1039/C8EE00001H.
Tsai, Ping-Chun, Wen, Bohua, Wolfman, Mark, Choe, Min-Ju, Pan, Menghsuan Sam, Su, Liang, Thornton, Katsuyo, Cabana, Jordi, and Chiang, Yet-Ming. Mon . "Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries". United Kingdom. doi:10.1039/C8EE00001H.
@article{osti_1426310,
title = {Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries},
author = {Tsai, Ping-Chun and Wen, Bohua and Wolfman, Mark and Choe, Min-Ju and Pan, Menghsuan Sam and Su, Liang and Thornton, Katsuyo and Cabana, Jordi and Chiang, Yet-Ming},
abstractNote = {The electrochemical kinetics of battery electrodes at the single-particle scale are measured as a function of state-of-charge, and interpreted with the aid of concurrent transmission X-ray microscopy (TXM) of the evolving particle microstructure. An electrochemical cell operating with near-picoampere current resolution is used to characterize single secondary particles of two widely-used cathode compounds, NMC333 and NCA. Interfacial charge transfer kinetics are found to vary by two orders of magnitude with state-of-charge (SOC) in both materials, but the origin of the SOC dependence differs greatly. NCA behavior is dominated by electrochemically-induced microfracture, although thin binder coatings significantly ameliorate mechanical degradation, while NMC333 demonstrates strongly increasing interfacial reaction rates with SOC for chemical reasons. Micro-PITT is used to separate interfacial and bulk transport rates, and show that for commercially relevant particle sizes, interfacial transport is rate-limiting at low SOC, while mixed-control dominates at higher SOC. These results provide mechanistic insight into the mesoscale kinetics of ion intercalation compounds, which can guide the development of high performance rechargeable batteries.},
doi = {10.1039/C8EE00001H},
journal = {Energy & Environmental Science},
number = 4,
volume = 11,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8EE00001H

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Cited by: 11 works
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