Self-Limiting Lithiation in Silicon Nanowires

Liu, Xiao Hua; Fan, Fenliang; Yang, Hui; Zhang, Sulin; Huang, Jianyu; Zhu, Ting

doi:10.1021/nn305282d

Cited by 223 publications

(244 citation statements)

References 49 publications

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“…4,6 The lithiationinduced compressive stress at the reaction front is expected to play a role in lowering the lithiation rate. 4,6 A systematic investigation of such retardation effect will be reported in a forthcoming publication.…”

Section: Numerical Resultsmentioning

confidence: 99%

See 1 more Smart Citation

A Phase-Field Model Coupled with Large Elasto-Plastic Deformation: Application to Lithiated Silicon Electrodes

Chen

Fan

Hong

et al. 2014

J. Electrochem. Soc.

111

105

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A phase-field model, accounting for large elasto-plastic deformation, is developed to study the evolution of phase, morphology and stress in crystalline silicon (Si) electrodes upon lithium (Li) insertion. The Li concentration profiles and deformation geometries are co-evolved by solving a set of coupled phase-field and mechanics equations using the finite element method. The present phase-field model is validated in comparison with a non-linear concentration-dependent diffusion model of lithiation in Si electrodes. It is shown that as the lithiation proceeds, the hoop stress changes from the initial compression to tension in the surface layer of the Si electrode, which may explain the surface cracking observed in experiments. The present phase-field model is generally applicable to high-capacity electrode systems undergoing both phase change and large elasto-plastic deformation. As a promising anode material for lithium (Li)-ion batteries, 1-3 the theoretical Li capacity of Silicon (Si) is 4200 mAh/g (corresponding to the lithiated phase of Li 4.4 Si), which is one order of magnitude larger than the commercialized graphite anode.1,2 Recent experiments revealed that the lithiation of crystalline Si (c-Si) occurs through a two-phase mechanism, i.e., growth of lithiated amorphous Li x Si (aLi x Si, x ∼ 3.75) phase separated from the unlithiated c-Si phase by a sharp phase boundary of about 1 nm thick.4-8 An abrupt change of Li concentration across the amorphous-crystalline interface (ACI) gives rise to drastic volume strain inhomogeneity. The resulting high stresses induce plastic flow, fracture, and pulverization of Si electrodes, thereby leading to the loss of electrical contact and limiting the cycle life of Li-ion batteries. [9][10][11] Electrochemically driven mechanical degradation in high-capacity electrodes has stimulated enormous efforts on the development of chemo-mechanical models to understand how the stress arises and evolves in lithiated Si electrodes.12-15 These chemo-mechanical models often treated the lithiation-induced stress as the diffusion-induced stress by considering Li diffusion in a solid-state electrode that results in the change of composition from its stoichiometric state. Deviation from stoichiometry usually results in a volume change that generates stress if the Li distribution is non-uniform. Early chemo-mechanical models only involved a unidirectional coupling. Namely, the diffusioninduced mechanical stress was considered, whereas the effect of mechanical stress on diffusion was ignored. Both experimental and computational studies, however, have shown that the mechanical stresses play an important role in the lithiation kinetics of Si electrodes. 4,6,16,17 Recently, fully coupled chemo-mechanical models were developed to incorporate the mechanical stress into the chemical potential. [18][19][20][21][22] In these models, the local stress modulates lithiation kinetics (reaction rate and diffusivity), 4,6,23 and in turn, lithiation kinetics regulates the stress generation in lithiated ...

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Section: Numerical Resultsmentioning

confidence: 99%

“…The sharp phase boundary plays a critical role in stress generation and fracture in c-Si during lithiation. 4,6 Hence, it is important to develop a fully coupled chemo-mechanical model to simulate the co-evolution of phase, morphology and stress during the lithiation process. …”

Section: Problem Descriptionmentioning

confidence: 99%

A Phase-Field Model Coupled with Large Elasto-Plastic Deformation: Application to Lithiated Silicon Electrodes

Chen

Fan

Hong

et al. 2014

J. Electrochem. Soc.

111

105

View full text Add to dashboard Cite

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“…The incompatible strain across the ACI suggests hydrostatic stress at the ACI and possibly in the lithiated shell. 79,87,91 The compressive stress slows down both Li diffusivity in the lithiation shell and the reaction rate at the ACI, leading to stress-mediated lithiation retardation, 84,92,93 as shown in Fig. 4a.…”

Section: Anisotropic Swelling and Fracture Of C-simentioning

confidence: 99%

Chemomechanical modeling of lithiation-induced failure in high-volume-change electrode materials for lithium ion batteries

Zhang

2017

npj Comput Mater

Self Cite

101

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The rapidly increasing demand for efficient energy storage systems in the last two decades has stimulated enormous efforts to the development of high-capacity, high-power, durable lithium ion batteries. Inherent to the high-capacity electrode materials is material degradation and failure due to the large volumetric changes during the electrochemical cycling, causing fast capacity decay and low cycle life. This review surveys recent progress in continuum-level computational modeling of the degradation mechanisms of high-capacity anode materials for lithium-ion batteries. Using silicon (Si) as an example, we highlight the strong coupling between electrochemical kinetics and mechanical stress in the degradation process. We show that the coupling phenomena can be tailored through a set of materials design strategies, including surface coating and porosity, presenting effective methods to mitigate the degradation. Validated by the experimental data, the modeling results lay down a foundation for engineering, diagnosis, and optimization of high-performance lithium ion batteries.

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“…At the interface, c-Si is transformed into a-Li and v < 5 nm/min, we obtain a c > 1 µm. A recent experimental study reports self-limiting lithiation behavior in Si nanowires, and the stress dependence of interface reaction rate or mobility is considered as a possible explanation 31 . However, there is no evidence so far to support that the stress effect on interface mobility is an important factor in the anisotropic swelling behavior of Si.…”

Section: Modelmentioning

confidence: 99%

Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design

Wood

et al. 2015

Phys. Chem. Chem. Phys.

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Although crystalline silicon (c-Si) anodes promise very high energy densities in Li-ion batteries, their practical use is complicated by amorphization, large volume expansion and severe plastic deformation upon lithium insertion. Recent experiments have revealed the existence of a sharp interface between crystalline Si (c-Si) and the amorphous Li x Si alloy during lithiation, which propagates with a velocity that is orientation dependent; the resulting anisotropic swelling generates substantial strain concentrations that initiate cracks even in nanostructured Si. Here we describe a novel strategy to mitigate lithiation-induced fracture by using pristine c-Si structures with engineered anisometric morphologies that are deliberately designed to counteract the anisotropy in the crystalline/amorphous interface velocity. This produces a much more uniform

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Self-Limiting Lithiation in Silicon Nanowires

Cited by 223 publications

References 49 publications

A Phase-Field Model Coupled with Large Elasto-Plastic Deformation: Application to Lithiated Silicon Electrodes

A Phase-Field Model Coupled with Large Elasto-Plastic Deformation: Application to Lithiated Silicon Electrodes

Chemomechanical modeling of lithiation-induced failure in high-volume-change electrode materials for lithium ion batteries

Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design

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