Vacancy diffusion and its consequences for void growth at the interface of a stripping metal electrode and solid electrolyte

It is commonly observed that voids can nucleate and grow in the lithium anode of a solid state Li-ion battery at a location adjacent to the solid electrolyte during the stripping (discharge) phase of the battery; a similar phenomenon is observed in sodium-based batteries. It is hypothesised in the current literature that the formation of these voids is due to the coalescence of vacancies that have been generated at the electrode/electrolyte interface when metal atoms are oxidized and transported into the electrolyte: the slow diffusion of the vacancies away from the electrolyte interface into the adjacent electrode results in their coalescence and the consequent growth of voids. These hypotheses are challenged in the current study by using the Onsager formalism to generate a variational principle for vacancy diffusion. Our analysis reveals that no driving force exists for the diffusion of vacancies into a homogeneous metal electrode that thins by stripping. This finding is contrary to models in the literature which have mistakenly assumed that the vanishing flux at the current collector prevents rigid body motion (drift) of the electrode which in turn prevents thinning of the electrode during stripping. Based on our analysis, we conclude that vacancy diffusion within a homogeneous electrode is not responsible for the nucleation and growth of voids at the interface between a stripping metal electrode and a solid electrolyte

Numerical simulation of the edge stress singularity and the adhesion strength for compliant mushroom fibrils adhered to rigid substrates

Bio-inspired adhesion of micropatterned surfaces due to intermolecular interactions has attracted much research interest over the last decade. Experiments show that the best adhesion is achieved with compliant “mushroom”-shaped fibrils. This paper analyses numerically the effects of different mushroom shapes on adhesion to a rigid substrate. When a remote stress is applied on the free end of a fibril perfectly bonded to a rigid substrate, the resultant stress distribution along the fibril is found to change dramatically between the straight punch and mushroom fibrils. A singular stress field is present at the edge of the fibril where it contacts the substrate and, in this work, the amplitude of the singularity is evaluated for fibrils perfectly bonded to a flat substrate so that sliding cannot occur there. This exercise is carried out for fibril geometries involving combinations of different diameters and thicknesses of the mushroom cap. By assuming a pre-existing detachment length at the corner where the stress singularity lies, we predict the adhesive strength for various mushroom cap shapes. Our study shows that a smaller stalk diameter and a thinner mushroom cap lead to higher adhesive strengths. A limited number of results are also given for other shapes, including those having a fillet radius connecting the stalk to the cap. The results support the rational optimization of synthetic micropatterned adhesives

Crystal Plasticity based Constitutive Model for Deformation in Metastable β Titanium Alloy

Acknowledgements Authors would like to acknowledge the funding received from university of Aberdeen for this project.Peer reviewe

Domain Switching as a Toughening Mechanism in Tetragonal Zirconia

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65640/1/j.1151-2916.1988.tb05943.x.pd

Influences of non-singular stresses on plane-stress near-tip fields for pressure-sensitive materials and applications to transformation toughened ceramics

In this paper, we investigate the effects of the non-singular stress ( T stress) on the mode I near-tip fields for elastic perfectly plastic pressure-sensitive materials under plane-stress and small-scale yielding conditions. The T stress is the normal stress parallel to the crack faces. The yield criterion for pressure-sensitive materials is described by a linear combination of the effective stress and the hydrostatic stress. Plastic dilatancy is introduced by the normality flow rule. The results of our finite element computations based on a two-parameter boundary layer formulation show that the total angular span of the plastic sectors of the near-tip fields increases with increasing T stress for materials with moderately large pressure sensitivity. The T stress also has significant effects on the sizes and shapes of the plastic zones. The height of the plastic zone increases substantially as the T stress increases, especially for materials with large pressure sensitivity. When the plastic strains are considered to be finite as for transformation toughened ceramics, the results of our finite element computations indicate that the phase transformation zones for strong transformation ceramics with large pressure sensitivity can be approximated by those for elastic-plastic materials with no limit on plastic strains. When the T stress and the stress intensity factor K are prescribed in the two-parameter boundary layer formulation to simulate the crack-tip constraint condition for a single-edge notch bend specimen of zirconia ceramics, our finite element computation shows a spear shape of the phase transformation zone which agrees well with the corresponding experimental observation.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/42782/1/10704_2004_Article_BF00018779.pd

Numerical investigation of 3-D constraint effects on brittle fracture in SE(B) and C(T) specimens

This investigation employs 3-D nonlinear finite element analyses to conduct an extensive parametric evaluation of crack front stress triaxiality for deep notch SE(B) and C(T) specimens and shallow notch SE(B) specimens, with and without side grooves. Crack front conditions are characterized in terms of J-Q trajectories and the constraint scaling model for cleavage fracture toughness proposed previously by Dodds and Anderson. The 3-D computational results imply that a significantly less strict size/deformation limit, relative to the limits indicated by previous plane-strain computations, is needed to maintain small-scale yielding conditions at fracture by a stress- controlled, cleavage mechanism in deep notch SE(B) and C(T) specimens. Additional new results made available from the 3-D analyses also include revised {eta}-plastic factors for use in experimental studies to convert measured work quantities to thickness average and maximum (local) J-values over the crack front

멱수법칙 크리프를 따르는 복합재료의 계면에서의 미끄러짐과 확산

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Cracking and associated volumetric expansion of NMC811 secondary particles

Secondary particles comprising a large number of nickel-rich single crystal primary particles are extensively used as storage particles in cathodes of lithium-ion batteries. It is well-established that crack formation in secondary particles is an important degradation mode that contributes to decline in battery performance. Recent X-ray tomographic observations suggest that, at very low C-rates, concentration gradients of lithium within an NMC811 secondary particle are negligible yet cracking still occurs. Additionally, during delithiation the primary particles shrink yet a volumetric expansion of the secondary particle occurs. These observations are explained by a numerical model of distributed cracking due to the extreme anisotropy of lithiation strain of primary particles. The incompatible deformation from grain to grain induces large self-stresses even in the absence of spatial gradients in the lithium concentration. The stress state is sufficient to drive a dynamic catastrophic fracture event, and the associated kinetic energy acquired by the primary particles moves them apart (akin to an explosive event) with the carbon and binder domain surrounding each secondary particle restricting the outward motion of the primary particles. It is predicted that a volume expansion of the secondary particles on the order of 20 % accompanies cracking, in agreement with recently reported observations