Grain-boundary fracture mechanisms in Li7La3Zr2O12 (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism

Monismith, Scott; Qu, Jianmin; Dingreville, Remi

doi:10.1016/j.jmps.2022.104791

Grain-boundary fracture mechanisms in Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism

Journal Article · Sat Jan 29 23:00:00 EST 2022 · Journal of the Mechanics and Physics of Solids

DOI:https://doi.org/10.1016/j.jmps.2022.104791· OSTI ID:1882865

^[1]; Qu, Jianmin ^[2]; ^[3]

Tufts Univ., Medford, MA (United States)
Tufts Univ., Medford, MA (United States); Stevens Institute of Technology, Hoboken, NJ (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Garnet-type, solid electrolytes, such as Li₇La₃Zr₂O₁₂ (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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1882865

Alternate ID(s):: OSTI ID: 1843873

Report Number(s):: SAND2022-0477J; 702563

Journal Information:: Journal of the Mechanics and Physics of Solids, Journal Name: Journal of the Mechanics and Physics of Solids Vol. 160; ISSN 0022-5096

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Grain-boundary fracture mechanisms in Li7La3Zr2O12 (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism

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Grain-boundary fracture mechanisms in Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes: When phase transformation acts as a temperature-dependent toughening mechanism