Electrochemical Stiffness Changes in Lithium Manganese Oxide Electrodes

Çapraz, Ömer Özgür; Bassett, Kimberly L.; Gewirth, Andrew A.; Sottos, Nancy R.

doi:10.1002/aenm.201601778

Electrochemical Stiffness Changes in Lithium Manganese Oxide Electrodes

Journal Article · Mon Dec 05 04:00:00 EST 2016 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201601778· OSTI ID:1392182

Çapraz, Ömer Özgür ^[1]; Bassett, Kimberly L. ^[2]; Gewirth, Andrew A. ^[2]; Sottos, Nancy R. ^[1]

Materials Science and Engineering 210 Materials Science &, Eng Bld, 1304 W. Green Urbana IL 61801 USA
Department of Chemistry University of Illinois A506 CLSL, Box 3‐6, 600 South Mathews Avenue Urbana IL 61801 USA

In situ strain and stress measurements are performed on composite electrodes to monitor potential‐dependent stiffness changes in lithium manganese oxide (LiMn ₂ O ₄ ). Lithium insertion and removal results in asynchronous strain and stress generation in the electrode. Electrochemical stiffness changes are calculated by combining coordinated stress and strain measurements. The electrode experiences dramatic changes in electrochemical stiffness due to potential‐dependent Li ⁺ ion intercalation mechanisms. The development of stress in the early stages of delithiation (at ≈3.95 V) due to a kinetic barrier at the electrode surface gives rise to stiffness changes in the electrode. Strain generation due to phase transformations reduces stiffness in the electrode at 4.17 V during delithiation and at 4.11 V during lithiation. During lithiation, stress generation due to Coulombic repulsions between occupied and incoming Li ⁺ ions leads to stiffening of the electrode at 3.96 V. The electrode also experiences greater changes in stiffness during delithiation compared to lithiation. These changes in electrochemical stiffness provide insight into the interplay between mechanical and electrochemical properties which control electrode response to lithiation and delithiation.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1392182

Alternate ID(s):: OSTI ID: 1388309

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 7 Vol. 7; ISSN 1614-6832

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

Country of Publication:: Germany

Language:: English

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