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:

Tsai, Ping-Chun ^[1]; Wen, Bohua  ^[2];

• Search DOE PAGES for author "Wen, Bohua"
• Search DOE PAGES for ORCID "0000-0002-8270-3396"

Wolfman, Mark  ^[3];

• Search DOE PAGES for author "Wolfman, Mark"
• Search DOE PAGES for ORCID "0000-0001-5746-2984"

Choe, Min-Ju  ^[4];

• Search DOE PAGES for author "Choe, Min-Ju"
• Search DOE PAGES for ORCID "0000-0002-0147-4887"

Pan, Menghsuan Sam ^[2]; Su, Liang ^[2]; Thornton, Katsuyo  ^[4];

• Search DOE PAGES for author "Thornton, Katsuyo"
• Search DOE PAGES for ORCID "0000-0002-1227-5293"

Cabana, Jordi  ^[3];

• Search DOE PAGES for author "Cabana, Jordi"
• Search DOE PAGES for ORCID "0000-0002-2353-5986"

Chiang, Yet-Ming  ^[2]

• Search DOE PAGES for author "Chiang, Yet-Ming"
• Search DOE PAGES for ORCID "0000-0002-0833-7674"

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+ Show Author Affiliations

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:

Mon Jan 01 00:00:00 EST 2018

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