Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

doi:10.1149/2.0071503jes

Title: Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

Journal Article · Tue Dec 09 00:00:00 EST 2014 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0071503jes· OSTI ID:1225867

Hudak, N. S. ^[1]; Davis, L. E. ^[1]; Nagasubramanian, G. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO₂ electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO₂. Despite significant losses in capacity upon cycling, neither cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO₂ structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO₂ electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1225867

Report Number(s):: SAND-2014-17923J; 537664

Journal Information:: Journal of the Electrochemical Society, Vol. 162, Issue 3; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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