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Porous Electrode Model with Particle Stress Effects for Li(Ni1/3Co1/3Mn1/3)O2 Electrode
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry.ORCID iD: 0000-0001-5768-7630
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering.ORCID iD: 0000-0002-8532-122X
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Applied Electrochemistry. COMSOL AB, Sweden.ORCID iD: 0000-0001-9627-1902
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering.ORCID iD: 0000-0003-4901-5820
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2019 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111Article in journal (Refereed) Published
Abstract [en]

A porous electrode model, incorporating particle stress effects, is developed for the electrode kinetic processes in the positive Li(Ni1/3Mn1/3Co1/3)O2 or NMC111 electrode. The model is used to analyze experimental data from galvanostatic intermittent titration technique (GITT) during charging at the beginning of life. The equilibrium potential accounts for the influence of mechanical stress in the electrode particles. While the standard Newman-based model proves unable to capture the dynamic performance of NMC111, the extended model with stress allows good fits of the GITT responses for NMC half cells for a voltage range from 3.7–4.1 V vs Li/Li+ at 10°C, 25°C and 40°C. Four physical parameters are extracted to analyze the underlying diffusive, kinetic, thermodynamic and stress phenomena from polarization to relaxation during a GITT transient. Strong dependencies of the kinetic rate constant k, slope of the open-circuit potential curve dEconc/dxpos and stress proportionality factor ϒstress with lithium concentration are found. The effective diffusion coefficients Ds,eff are ∼10−14 – 10−13 cm2/s across voltages and temperatures. Diffusion limitation and particle surface stress are more profound at higher voltages and at higher temperatures. This leads to large lithium concentration gradient near particle surface, requiring longer relaxation time during GITT.

Place, publisher, year, edition, pages
2019.
Keywords [en]
Batteries - Lithium, Electrode Kinetics
National Category
Engineering and Technology
Identifiers
URN: urn:nbn:se:kth:diva-256548DOI: 10.1149/2.0661913jesISI: 000483501000003Scopus ID: 2-s2.0-85073684103OAI: oai:DiVA.org:kth-256548DiVA, id: diva2:1346479
Note

QC 20190903

Available from: 2019-08-28 Created: 2019-08-28 Last updated: 2020-02-20Bibliographically approved

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Ko, Jing YingVarini, MariaEkström, HenrikKlett, MatildaLindbergh, Göran

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