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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.
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.
The mechanics of detachment is analysed for 2 D flat-bottomed planar pillars and 3 D cylindrical pillars from a dissimilar elastic substrate. Application of an axial stress to the free end of the pillar results in a singularity in stress at the corner with the substrate. An eigenvalue analysis reveals that the stress field near the corner is dominated by two singular eigenfields having eigenvalues (λ 1 ,λ 2 ) with corresponding intensities (H 1 ,H 2 ). The asymptotic stress field σ ij is of the form σ ij = H 1 r λ1-1 f ij (λ 1 , θ)+H 2 r λ2−1 f ij (λ 2 , θ) , where f ij describe the angular dependence θ of σ ij , and r is the radial distance from the corner. The stress intensities (H 1 ,H 2 ) are calculated numerically, using a domain integral approach, as a function of the elastic mismatch between the pillar and substrate. The singular zone extends across approximately 10% of the pillar diameter (in 3 D) or pillar width (in 2 D). Interfacial failure is predicted for an assumed crack emanating from the corner of pillar and substrate. For the case of an interfacial crack that resides within the domain of corner singularity, a boundary layer analysis is performed to calculate the dependence of the interfacial stress intensity factor K upon (H 1 ,H 2 ). When the crack extends beyond the domain of corner singularity, it is necessary to consider the full geometry in order to obtain K. A case study explores the sensitivity of the pull-off stress to the flaw size and to the degree of material mismatch. The study has implications for the optimum design of adhesive surface micropatterns, for bonding to either stiffer or more compliant substrates.
The adhesion of micron-scale surfaces due to intermolecular interactions is a subject of intense interest spanning electronics, biomechanics and the application of soft materials to engineering devices. The degree of adhesion is sensitive to the diameter of micro-pillars in addition to the degree of elastic mismatch between pillar and substrate. Adhesion-strength-controlled detachment of an elastic circular cylinder from a dissimilar substrate is predicted using a Dugdale-type of analysis, with a cohesive zone of uniform tensile strength emanating from the interface corner. Detachment initiates when the opening of the cohesive zone attains a critical value, giving way to crack formation. When the cohesive zone size at crack initiation is small compared to the pillar diameter, the initiation of detachment can be expressed in terms of a critical value Hc of the corner stress intensity. The estimated pull-off force is somewhat sensitive to the choice of stick/slip boundary condition used on the cohesive zone, especially when the substrate material is much stiffer than the pillar material. The analysis can be used to predict the sensitivity of detachment force to the size of pillar and to the degree of elastic mismatch between pillar and substrate.
Nature uses hierarchical fibrillar structures to mediate temporary adhesion to arbitrary substrates. Such structures provide high compliance such that the flat fibril tips can be better positioned with respect to asperities of a wavy rough substrate. We investigated the buckling and adhesion of hierarchically structured adhesives in contact with flat smooth, flat rough and wavy rough substrates. A macroscopic model for the structural adhesive was fabricated by molding polydimethylsiloxane into pillars of diameter in the range of 0.3–4.8 mm, with up to three different hierarchy levels. Both flat-ended and mushroom-shaped hierarchical samples buckled at preloads one quarter that of the single level structures. We explain this behavior by a change in the buckling mode; buckling leads to a loss of contact and diminishes adhesion. Our results indicate that hierarchical structures can have a strong influence on the degree of adhesion on both flat and wavy substrates. Strategies are discussed that achieve highly compliant substrates which adhere to rough 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 optimisation of synthetic micropatterned adhesives.
The break-up of a nanowire with an organic ligand shell into discrete droplets is analysed in terms of the Rayleigh-Plateau instability. Explicit account is taken of the effect of the organic ligand shell upon the energetics and kinetics of surface diffusion in the wire. Both an initial perturbation analysis and a full numerical analysis of the evolution in wire morphology are conducted, and the governing non-dimensional groups are identified. The perturbation analysis is remarkably accurate in obtaining the main features of the instability, including the pinch-off time and the resulting diameter of the droplets. It is conjectured that the surface energy of the wire and surrounding organic shell depends upon both the mean and deviatoric invariants of the curvature tensor. Such a behaviour allows for the possibility of a stable nanowire such that the Rayleigh-Plateau instability is not energetically favourable. A stability map illustrates this. Maps are also constructed for the final droplet size and pinch-off time as a function of two non-dimensional groups that characterise the energetics and kinetics of diffusion in the presence of the organic shell. These maps can guide future experimental activity on the stabilisation of nanowires by organic ligand shells.
The relative tendency of freely dispersed and bundled gold nanowires to break up along their length by the Rayleigh–Plateau instability is investigated both experimentally and theoretically. Small angle X-ray scattering, in combination with transmission electron microscopy, reveal that the bundling of nanowires can enhance their stability. The experimental observation is rationalized by a linear perturbation analysis of a representative unit cell of bundled wires. A stability map is constructed for a bundle of nanowires to display the sensitivity of the Rayleigh–Plateau instability to the number and size of contacts with nearest neighbors per nanowire, and to the ratio of interfacial energy to surface energy. Stabilisation is enhanced by allowing the bundle of wires to sinter freely: a criterion for this kinetically-based stabilisation is given in terms of the ratio of pinch-off time for the instability to the sintering time to form the necks between nanowires.
© 2020 Lithium-ion batteries with single ion-conductor ceramic electrolytes short-circuit when subjected to charging currents above a critical current density. Here, we analyse the rate at which a lithium (Li) filament (sometimes referred to as a dendrite) will grow from the cathode towards the anode during charging of such batteries. The filament is modelled as a climbing edge dislocation with its growth occurring by Li+ flux from the electrolyte into the filament tip at constant chemical potential. The growth rate is set by a balance between the reduction of free-energy at the filament tip and energy dissipation associated with the resistance to the flux of Li+ through the filament tip. For charging currents above the critical current density, the filament growth rate increases with decreasing filament tip resistance. Imperfections, such as voids in the Li cathode along the electrolyte/cathode interface, decrease the critical current density but filament growth rates are also lower in these cases as filament growth rates scale with the charging currents. The predictions of the model are in excellent quantitative agreement with measurements and confirm that above the critical current density a filament can traverse the electrolyte in minutes or less. This suggests that initiation of filament growth is the critical step to prevent short-circuiting of the battery.
