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Abstract Mechanical failure and its interference with electrochemistry are a roadblock in deploying high-capacity electrodes for Li-ion batteries. Computational prediction of the electrochemomechanical behavior of high-capacity composite electrodes is a significant challenge because of (i) complex interplay between mechanics and electrochemistry in the form of stress-regulated Li transport and interfacial charge transfer, (ii) thermodynamic solution non-ideality, (iii) nonlinear deformation kinematics and material inelasticity, and (iv) evolving material properties over the state of charge. We develop a computational framework that integrates the electrochemical response of batteries modulated by large deformation, mechanical stresses, and dynamic material properties. We use silicon as a model system and construct a microstructurally resolved porous composite electrode model. The model concerns the effect of large deformation of silicon on charge conduction and electrochemical response of the composite electrode, impact of mechanical stress on Li transport and interfacial charge transfer, and asymmetric charging/discharging kinetics. The study captures the rate-dependent, coupled electrochemomechanical behavior of high-capacity composite electrodes that agrees well with experimental results.
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Computational Modeling of Heterogeneity of Stress, Charge, and Cyclic Damage in Composite Electrodes of Li-Ion Batteries
Charge heterogeneity is a prevalent feature in many electrochemical systems. In a commercial cathode of Li-ion batteries, the composite is hierarchically structured across multiple length scales including the sub-micron single-crystal primary-particle domains up to the macroscopic particle ensembles. The redox kinetics of charge transfer and mass transport strongly couples with mechanical stresses. This interplay catalyzes substantial heterogeneity in the charge (re)distribution, stresses, and mechanical damage in the composite electrode during charging and discharging. We assess the heterogeneous electrochemistry and mechanics in a LiNixMnyCozO2(NMC) cathode using a fully coupled electro-chemo-mechanics model at the cell level. A microstructure-resolved model is constructed based on the synchrotron X-ray tomography data. We calculate the stress field in the composite and then quantitatively evaluate the kinetics of surface charge transfer and Li transport biased by mechanical stresses. We further model the cyclic behavior of the cell. The repetitive deformation of the active particles and the weakening of the interfacial strength cause gradual increase of the interfacial debonding. The mechanical damage impedes electron transfer, incurs more charge heterogeneity, and results in the capacity degradation in batteries over cycles.
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- PAR ID:
- 10360482
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 167
- Issue:
- 4
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- Article No. 040527
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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