Multiscale Chemo-mechanical Mechanics of High-capacity Anode Materials in Lithium-ion Nano-batteries

Open Access
Yang, Hui
Graduate Program:
Engineering Science and Mechanics
Doctor of Philosophy
Document Type:
Date of Defense:
October 08, 2014
Committee Members:
  • Sulin Zhang, Dissertation Advisor
  • Sulin Zhang, Committee Chair
  • Charles E Bakis, Committee Member
  • Long Qing Chen, Committee Member
  • Adrianus C Van Duin, Committee Member
  • Lithium-ion battery
  • Anode materials
  • Chemomechanical modeling
  • Diffusion
  • Orientation-dependent interfacial mobility
  • Fracture
Rechargeable lithium-ion batteries (LIBs), which are the most prevailing and promising electrochemical energy storage and conversion devices due to their high energy density and design flexibility, are widely used in portable electronics and electric vehicles. Currently commercialized LIBs adopt graphite as anode for its long cycle life, abundant material supply, and relatively low cost. However, graphite suffers low specific charge capacity (372 mAhg−1), which is obviously insufficient for powering new generation electronic devices. Thus, considerable efforts are being undertaking to develop alternative anode materials with low cost, high capacity, and long cycle life. A variety of high capacity anode materials have been identified, and silicon (Si) stands as the leading candidate and has attracted much attention for its highest theoretical capacity (4200 mAhg−1). Nevertheless, inherent to the high-capacity electrodes, lithium (Li) insertion-extraction cycling induces huge volumetric expansion and stress inside the electrodes, leading to fracture, pulverization, electrical disconnectivity, and ultimately huge capacity loss. Therefore, a fundamental understanding of the degradation mechanisms in the high-capacity anodes during lithiation-delithiation cycling is crucial for the rational design of next-generation failure-resistant electrodes. In this thesis, a finite-strain chemo-mechanical model is formulated to study the lithiation-induced phase transformation, morphological evolution, stress generation and fracture in high capacity anode materials such as Si and germanium (Ge). The model couples Li reaction-diffusion with large elasto-plastic deformation in a bidirectional manner: insertion of the Li into electrode generates localized stress, which in turn mediates electrochemical insertion rates. Several key features observed from recent transmission electron microscopy (TEM) studies are incorporated into the modeling framework, including the sharp interface between the lithiated amorphous shell and unlithiated crystalline core, crystallographic orientation-dependent electrochemical reaction rate, and large-strain plasticity. The simulation results demonstrate that the model faithfully predicts the anisotropic swelling of lithiated crystalline silicon nanowires (c-SiNWs) observed from previous experimental studies. Stress analysis reveals that the SiNWs are prone to surface fracture at the angular sites where two adjacent facets intersect, consistent with previous experimental observations. In addition, Li insertion can induce high hydrostatic pressure at and closely behind the reaction front, which can lead to the lithiation retardation observed by TEM studies. For a comparative study, the highly reversible expansion and contraction of crystalline germanium nanoparticles (c-GeNPs) under lithiation-delithiation cycling are reported. During multiple cycles to the full capacity, the GeNPs remain robust without any visible cracking despite ~260% volume changes, in contrast to the size dependent fracture of crystalline silicon nanoparticles (c-SiNPs) upon the first lithiation. The comparative study of c-SiNPs, c-GeNPs, and amorphous SiNPs (a-SiNPs) through in-situ TEM and chemo-mechanical modeling suggest that the tough behavior of c-GeNPs and a-SiNPs can be attributed to the weak lithiation anisotropy at the reaction front. In the absence of lithiation anisotropy, the c-GeNPs and a-SiNPs experience uniform hoop tension in the surface layer without the localized high stress and therefore remain robust throughout multicycling. In addition, the two-step lithiation in a-SiNPs can further alleviate the abruptness of the interface and hence the incompatible stress at the interface, leading to an even tougher behavior of a-SiNPs. Therefore, eliminating the lithiation anisotropy presents a novel pathway to mitigate the mechanical degradation in high-capacity electrode materials. In addition to the study of the retardation effect caused by lithiation self-generated internal stress, the influence of the external bending on the lithiation kinetics and deformation morphologies in germanium nanowires (GeNWs) is also investigated. Contrary to the symmetric core-shell lithiation in free-standing GeNWs, bending a GeNW during lithiation breaks the lithiation symmetry, speeding up lithaition at the tensile side while slowing down at the compressive side of the GeNWs. The chemo-mechanical modeling further corroborates the experimental observations and suggests the stress dependence of both Li diffusion and interfacial reaction rate during lithiation. The finding that external load can mediate lithiation kinetics opens new pathways to improve the performance of electrode materials by tailoring lithiation rate via strain engineering. Furthermore, in the light of bending-induced symmetry breaking of lithiation, the mechanically controlled flux of the secondary species (i.e., Li) features a novel energy harvesting mechanism through mechanical stress. Besides the continuum level chemo-mechanical modelings, molecular dynamics simulations with the ReaxFF reactive force field are also conducted to investigate the fracture mechanisms of lithiated graphene. The simulation results reveal that Li diffusion toward the crack tip is both energetically and kinetically favored owing to the crack-tip stress gradient. The stress-driven Li diffusion results in Li aggregation around the crack tip, chemically weakening the crack-tip bond and at the same time causing stress relaxation. As a dominant factor in lithiated graphene, the chemical weakening effect manifests a self-weakening mechanism that causes the fracture of the graphene. Moreover, lithiation-induced fracture mechanisms of defective single-walled carbon nanotubes (SWCNTs) are elucidated by molecular dynamics simulations. The variation of defect size and Li concentration sets two distinct fracture modes of the SWCNTs upon uniaxial stretch: abrupt and retarded fracture. Abrupt fracture either involves spontaneous Li weakening of the propagating crack tip or is absent of Li participation, while retarded fracture features a “wait-and-go” crack extension process in which the crack tip periodically arrests and waits to be weakened by diffusing Li before extension resumes. The failure analysis of the defective CNTs upon lithiation, together with the cracked graphene, provides fundamental guidance to the lifetime extension of high capacity anode materials.