Stress Corrosion Cracking of Austenitic Stainless Steels: Correlating in-situ crack tip chemistry and crack growth rate measurements.
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New continuum and dimensional extension to published work by Scott Grutzik and Michael Buche.
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23rd International Conference on Solid State Ionics (SSI-23), Boston, MA, July 17-22, 2022
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The influence of the external cathodic area, stress intensity, and electrochemical polarization level on the resultant crack growth rate and crack tip pH and potential was studied for stainless steel 304L in a sodium chloride environment. Before testing, the validity of in situ crack tip property measurements using microprobes and drilled holes was supported through modeling efforts and confirmed with experimental observations. Here, it was found that increasing the R-ratio during corrosion fatigue increased the crack growth rate and decreased the measured crack tip pH of the 304L sample. Decreasing the electrochemical potential (i.e., cathodic polarization) of the bulk sample increased the crack tip pH and stopped measured crack extension under constant K conditions. Conversely, increasing the potential of the bulk sample decreased the crack tip pH and induced cracking under constant K conditions. Decreasing the cathodic area external to the crack increased the measured pH at the crack tip and decreased the crack growth rate under fatigue conditions. For the given configuration, environment, and alloy studied, fatigue crack growth is not sustained by cathodic reactions solely occurring in the crack wake and notch. These results have implications for the ability to predict atmospheric crack growth rates from laboratory, full immersion experiments.
Dendrite growth and crack propagation are two major hurdles on the road towards the large-scale commercialization of lithium metal all-solid-state batteries (ASSBs). Due to the high multiphysics coupled nature of the underlying dendrite growth mechanism, understanding it has been difficult. Herein, for the first time, an electrochemical-mechanical model is established that directly couples dendrite growth and crack propagation from a physics-based perspective at the cell level. Results reveal that overpotential-driven stress propels a crack to penetrate through the solid electrolyte, creating vacancies for dendrite growth, leading to the short circuit of the battery. Thus, high lithiation/charging rate and low conductivity of electrolytes can accelerate the electrochemical failure of the battery. It is further discovered that Young's modulus E LLZO of the electrolyte has competing contributions to the fracture and dendrite growth; specifically, when E LLZO = 40-100 GPa, the short circuit is triggered early. A larger toughness value hinders the crack propagation and mitigates the Li dendrite growth. The developed multiphysics model provides an in-depth understanding of the coupling of crack propagation and dendrite growth within ASSBs and an insightful mechanistic design guidance map for robust and safe ASSB cells.