Abstract One key barrier to using lithium‐metal anode batteries is that metal dendrites can penetrate solid electrolytes, causing short‐circuits and battery failures. It is established that this failure is likely caused by crack propagation due to electrodeposition‐induced stresses from lithium metal. This study explores ways to harness these electrochemical‐mechanical couplings to control dendrite growth and improve battery reliability using a phase‐field model and targeted fracture experiments. The results show that dendrite growth can be effectively mitigated by applying mechanical stresses or tailoring the material's fracture toughness. This study also outlines the requirements for compressive stress to halt or deflect dendrites as a function of the overpotential and discusses the role of microstructure in this process.

Monismith, Scott↗

DOE OSTI2023

Electrochemically induced fracture in LLZO: How the interplay between flaw density and electrostatic potential affects operability

Fracture and short circuit in the Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte are two key issues that prevent its adoption in battery cells. In this paper, we utilize phase-field simulations that couple electrochemistry and fracture to evaluate the maximum electric potential that LLZO electrolytes can support as a function of crack density. In the case of a single crack, we find that the applied potential at the onset of crack propagation exhibits inverse square root scaling with respect to crack length, analogous to classical fracture mechanics. Here, we further find that the short-circuit potential scales linearly with crack length. In the realistic case where the solid electrolyte contains multiple cracks, we reveal that failure fits the Weibull model. The failure distributions shift to favor failure at lower overpotentials as areal crack density increases. Furthermore, when flawless interfacial buffers are placed between the applied potential and the bulk of the electrolyte, failure is mitigated. When constant currents are applied, current focuses in near-surface flaws, leading to crack propagation and short circuit. We find that buffered samples sustain larger currents without reaching unstable overpotentials and without failing. Our findings suggest several mitigation strategies for improving the ability of LLZO to support larger currents and improve operability.

25 ENERGY STORAGE↗

DOE OSTI2022

Use of a non-collinear wave mixing technique to image internal microscale damage in concrete

This research demonstrates the feasibility of using a non-collinear wave mixing technique to image internal microscale damage throughout the interior volume of a relatively large (28 cm thick) concrete component. By exploiting the underlying mechanics of nonlinear wave mixing, it is possible to mix two incident waves with frequencies low enough to propagate without being scattered by the inherently heterogenous, concrete microstructure, while still being sensitive to damage features with length scales well below these incident wavelengths. For this study, scanning and imaging is accomplished by manually adjusting the locations of the two incident waves, while a knowledge of the wave speeds in concrete plus synchronization identifies the location of the mixing zone—the specific volume of concrete being imaged. The viability of the proposed technique is demonstrated by examining a concrete prism specimen with known, embedded internal microscale damage.

Kim, Jin-Yeon (ORCID:0000000255180032)↗

DOE OSTI2022

Grain-boundary fracture mechanisms in Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism

Garnet-type, solid electrolytes, such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising alternative to liquid electrolytes for lithium-metal batteries. However, such solid-electrolyte materials frequently exhibit undesirable lithium (Li) metal plating and fracture along grain boundaries. In this work, we employ atomistic simulations to investigate the mechanisms and key fracture properties associated with intergranular fracture along one such boundary. Our results show that, in the case of a Σ5 (310) grain boundary, this boundary exhibits brittle fracture behavior, i.e. the absence of dislocation activity ahead of the propagating crack tip, accompanied with a decrease in work of separation, peak stress, and maximum stress intensity factor as the temperature increases from 300 K to 1500 K. As the crack propagates, we predict two temperature-dependent Li clustering regimes. For temperatures at or below 900 K, Li tends to cluster in the bulk region away from the crack plane driven by a void-coalescence mechanism concomitant a simultaneous cubic-to-tetragonal phase transition. The tetragonalization of LLZO in this temperature regime acts as an emerging toughening mechanism. At higher temperatures, this phase transition mechanism is suppressed leading to a more uniform distribution of Li throughout the grain-boundary system and lower fracture properties as compared to lower temperatures.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Analytical modeling of the evolution of the nonlinearity parameter of sensitized stainless steel

Austenitic stainless steels are subject to the precipitation of chromium carbides (M 23 C 6 ) during exposure to high temperatures, causing these alloys to be susceptible to intergranular corrosion due to chromium depletion along grain boundaries. The acoustic nonlinearity parameter, β, shows sensitivity to the formation of carbides in these alloys. The Thermo-Calc TC-PRISMA module was used to model the nucleation and growth of grain boundary M 23 C 6 carbides. The model was verified with scanning transmission electron microscopy analysis that allowed measurements of the grain boundary precipitates. The paper introduces a reduced-order model of the acoustic nonlinearity based on the formation of misfit dislocations at the interface of the grain boundary precipitate and matrix to explain the change in β during isothermal aging. Furthermore, a direct relationship between the radius of the M 23 C 6 grain boundary carbides and β was observed and verified with nonlinear ultrasound measurements on 304L and 316L stainless steels.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Stress-induced transition from vacancy annihilation to void nucleation near microcracks

Not Available

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

Necessary and sufficient conditions for resonant mixing of plane waves in elastic solids with quadratic nonlinearity

This paper studies the interactions of two plane waves in elastic solids with quadratic nonlinearity. In particular, the necessary and sufficient conditions for resonant mixing of two plane waves are derived. It is shown that the conventional resonance condition for resonant mixing of plane waves is only a necessary condition, not sufficient. Based on the newly derived necessary and sufficient conditions, resonant mixing of various types of plane waves are investigated and specific conditions for generating a resonant mixed wave are obtained for each case. These results are useful for developing nonlinear ultrasonic nondestructive evaluation techniques using the wave mixing method.

Gao, Xiang↗

NASA NTRS1999

Ultrasonic Nondestructive Characterization of Adhesive Bonds

Adhesives and adhesive joints are widely used in various industrial applications to reduce weight and costs, and to increase reliability. For example, advances in aerospace technology have been made possible, in part, through the use of lightweight materials and weight-saving structural designs. Joints, in particular, have been and continue to be areas in which weight can be trimmed from an airframe through the use of novel attachment techniques. In order to save weight over traditional riveted designs, to avoid the introduction of stress concentrations associated with rivet holes, and to take full advantage of advanced composite materials, engineers and designers have been specifying an ever-increasing number of adhesively bonded joints for use on airframes. Nondestructive characterization for quality control and remaining life prediction has been a key enabling technology for the effective use of adhesive joints. Conventional linear ultrasonic techniques generally can only detect flaws (delamination, cracks, voids, etc) in the joint assembly. However, more important to structural reliability is the bond strength. Although strength, in principle, cannot be measured nondestructively, a slight change in material nonlinearity may indicate the onset of failure. Furthermore, microstructural variations due to aging or under-curing may also cause changes in the third order elastic constants, which are related to the ultrasonic nonlinear parameter of the polymer adhesive. It is therefore reasonable to anticipate a correlation between changes in the ultrasonic nonlinear acoustic parameter and the remaining bond strength. It has been observed that higher harmonics of the fundamental frequency are generated when an ultrasonic wave passes through a nonlinear material. It seems that such nonlinearity can be effectively used to characterize bond strength. Several theories have been developed to model this nonlinear effect. Based on a microscopic description of the nonlinear interface binding force, a quantitative method was presented. Recently, a comparison between the experimental and simulated results based on a similar theoretical model was presented. A through-transmission setup for water immersion mode-converted shear waves was used to analyze the ultrasonic nonlinear parameter of an adhesive bond. In addition, ultrasonic guided waves have been used to analyze adhesive or diffusion bonded joints. In this paper, the ultrasonic nonlinear parameter is used to characterize the curing state of a polymer/aluminum adhesive joint. Ultrasonic through-transmission tests were conducted on samples cured under various conditions. The magnitude of the second order harmonic was measured and the corresponding ultrasonic nonlinear parameter was evaluated. A fairly good correlation between the curing condition and the nonlinear parameter is observed. The results show that the nonlinear parameter might be used as a good indicator of the cure state for adhesive joints.

Qu, Jianmin↗

NASA NTRS1997

Ultrasonic Nondestructive Characterization of Adhesive Bonds

Qualitative measurements of adhesion or binding forces can be accomplished, for example, by using the reflection coefficient of an ultrasound or by using thermal waves (Light and Kwun, 1989, Achenbach and Parikh, 1991, and Bostrom and wickham, 1991). However, a quantitative determination of binding forces is rather difficult. It has been observed that higher harmonics of the fundamental frequency are generated when an ultrasound passes through a nonlinear material. It seems that such non-linearity can be effectively used to characterize the bond strength. Several theories have been developed to model this nonlinear effect (Adler and Nagy, 1991; Achenbach and Parikh, 1991; Parikh and Achenbach, 1992; and Hirose and Kitahara, 1992; Anastasi and Roberts, 1992). Based on a microscopic description of the nonlinear interface binding force, a quantitative method was presented by Pangraz and Arnold (1994). Recently, Tang, Cheng and Achenbach (1997) made a comparison between the experimental and simulated results based on this theoretical model. A water immersion mode-converted shear wave through-transmission setup was used by Berndt and Green (1997) to analyze the nonlinear acoustic behavior of the adhesive bond. In this project, the nonlinear responses of an adhesive joint was investigated through transmission tests of ultrasonic wave and analyzed by the finite element simulations. The higher order harmonics were obtained in the tests. It is found that the amplitude of higher harmonics increases as the aging increases, especially the 3dorder harmonics. Results from the numerical simulation show that the material nonlinearity does indeed generate higher order harmonics. In particular, the elastic-perfect plastic behavior generates significant 3rd and 5th order harmonics.

Qu, Jianmin↗

NASA NTRS1989

Reciprocal relations for transmission coefficients - Theory and application

The authors present a rigorous proof of certain intuitively plausible reciprocal relations for time harmonic plane-wave transmission and reflection at the interface between a fluid and an anisotropic elastic solid. Precise forms of the reciprocity relations for the transmission coefficients and for the transmitted energy fluxes are derived, based on the reciprocity theorem of elastodynamics. It is shown that the reciprocity relations can be used in conjunction with measured values of peak amplitudes for transmission through a slab of the solid (water-solid-water) to obtain the water-solid coefficients. Experiments were performed for a slab of a unidirectional fiber-reinforced composite. Good agreement of the experimentally measured transmission coefficients with theoretical values was obtained.

Qu, Jianmin↗