Li Penetration in Ceramic Solid Electrolytes: Operando Microscopy Analysis of Morphology, Propagation, and Reversibility

Kazyak, Eric; Garcia‐Mendez, Regina; LePage, William S.; Sharafi, Asma; Davis, Andrew L.; Sanchez, Adrian J.; Chen, Kuan‐Hung; Haslam, Catherine G.; Sakamoto, Jeff; Dasgupta, Neil P.

doi:10.1016/j.matt.2020.02.008

Cited by 314 publications

(378 citation statements)

References 51 publications

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“…Similar phenomena is also observed in SEM images recently reported. [ 18 ] As shown in Figure 4d–f, these unfilled voids preferentially appeared at positions where the crack was templated along a different grain orientation or in regions of relatively large curvature. Therefore, to a significant extent, the grain structure controlled the crack shape, which in turn influenced the distribution of lithium and the residual voids inside cracks.…”

Section: Resultsmentioning

confidence: 98%

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

Hao

Bailey

Iacoviello

et al. 2020

Adv Funct Materials

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Solid‐state lithium batteries will revolutionize the lithium‐ion battery and energy storage applications if certain key challenges can be resolved. The formation of lithium‐protrusions (dendrites) that can cause catastrophic short‐circuiting is one of the main obstacles, and progresses by a mechanism that is not yet fully understood. By utilizing X‐ray computed tomography with nanoscale resolution, the 3D morphology of lithium protrusions inside short‐circuited solid electrolytes has been obtained for the first time. Distinguishable from adjacent voids, lithium protrusions partially filled cracks that tended to propagate intergranularly through the solid electrolyte, forming a large waved plane in the shape of the grain boundaries. Occasionally, the lithium protrusions bifurcate into flat planes in a transgranular mode. Within the cracks themselves, lithium protrusions are preferentially located in regions of relatively low curvature. The crack volume filled with lithium in two samples is 82.0% and 83.1%, even though they have distinctly different relative densities. Pre‐existing pores in the solid electrolyte, as a consequence of fabrication, can also be part‐filled with lithium, but do not have a significant influence on the crack path. The crack/lithium‐protrusion behavior qualitatively supports a model of propagation combining electrochemical and mechanical effects.

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Section: Resultsmentioning

confidence: 98%

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

Hao

Bailey

Iacoviello

et al. 2020

Adv Funct Materials

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“…This is also in agreement with macroscopic measurements on polycrystalline garnet samples, which also showed an involvement of transgranular fracture on the cell short circuits. [56][57][58] In addition, preferred growth along the grain boundary regions [59] as well as growth through interconnected pores [60,61] in pellets with open porosity are reported failure modes.…”

Section: Li|llzo Electrodeposition Kineticsmentioning

confidence: 99%

The Fast Charge Transfer Kinetics of the Lithium Metal Anode on the Garnet‐Type Solid Electrolyte Li_6.25Al_0.25La₃Zr₂O₁₂

Krauskopf

Mogwitz

Hartmann

et al. 2020

Advanced Energy Materials

139

136

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The charge transfer kinetics between a lithium metal electrode and an inorganic solid electrolyte is of key interest to assess the rate capability of future lithium metal solid state batteries. In an in situ microelectrode study run in a scanning electron microscope, it is demonstrated that—contrary to the prevailing opinion—the intrinsic charge transfer resistance of the Li|Li6.25Al0.25La3Zr2O12 (LLZO) interface is in the order of 10−1 Ω cm2 and thus negligibly small. The corresponding high exchange current density in combination with the single ion transport mechanism (t+ ≈ 1) of the inorganic solid electrolyte enables extremely fast plating kinetics without the occurrence of transport limitations. Local plating rates in the range of several A cm−2 are demonstrated at defect free and chemically clean Li|LLZO interfaces. Practically achievable current densities are limited by lateral growth of lithium along the surface as well as electro‐chemo‐mechanical‐induced fracture of the solid electrolyte. In combination with the lithium vacancy diffusion limitation during electrodissolution, these morphological instabilities are identified as the key fundamental limitations of the lithium metal electrode for solid‐state batteries with inorganic solid electrolytes.

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“…current density) which suggests that there are a variety of failure mechanisms. 9 Transmission electron microscopy imaging has revealed nanometer level tetragonal LLZO interphase formation at the Li|cubic-LLZO interface. 24 Interphase formation can also induce mechanical stresses due to volume expansion leading to chemo-mechanical failure.…”

mentioning

confidence: 99%

Synchrotron Imaging of Li Metal Anodes in Solid State Batteries Aided by Machine Learning

Dixit¹,

Verma²,

Zaman³

et al. 2020

Preprint

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Reversible lithium metal anodes that can achieve high rate capabilities are necessary for next generation energy storage systems. Solid electrolyte can act as a barrier for unwanted physical and chemical decomposition that lead to unstable electrodeposition (e.g. dendrite and filament growth). The formation and growth of filaments is tied to unique chemo-mechanical properties that exists at buried solid|solid interfaces. Herein,<i> in situ</i> tomography of Li|LLZO|Li cells is carried out to track morphological transformations in Li metal electrodes and buried solid|solid interfaces during stripping and plating processes. Optimized experimental parameters provide high resolution, high contrast reconstructions that enable lithium metal visualization. Machine learning and image processing tools are combined to quantify changes in lithium metal during stripping and plating. The analysis enables quantifying local current densities and pore size distribution in lithium metal during cycling experiments. Hotspots in lithium metal are correlated with microstructural anisotropy in the solid electrolyte. Modeling studies show large heterogeneity in transport and mechanical properties of electrolyte at the electrode|electrolyte interfaces. Regions with lower effective properties (transport and mechanical) are nuclei for failure. Failure is attributed to microstructural heterogeneities in the solid electrolyte that lead to high local stress and flux distributions.

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Li Penetration in Ceramic Solid Electrolytes: Operando Microscopy Analysis of Morphology, Propagation, and Reversibility

Cited by 314 publications

References 51 publications

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

The Fast Charge Transfer Kinetics of the Lithium Metal Anode on the Garnet‐Type Solid Electrolyte Li_6.25Al_0.25La₃Zr₂O₁₂

Synchrotron Imaging of Li Metal Anodes in Solid State Batteries Aided by Machine Learning

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Li Penetration in Ceramic Solid Electrolytes: Operando Microscopy Analysis of Morphology, Propagation, and Reversibility

Cited by 314 publications

References 51 publications

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

The Fast Charge Transfer Kinetics of the Lithium Metal Anode on the Garnet‐Type Solid Electrolyte Li6.25Al0.25La3Zr2O12

Synchrotron Imaging of Li Metal Anodes in Solid State Batteries Aided by Machine Learning

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The Fast Charge Transfer Kinetics of the Lithium Metal Anode on the Garnet‐Type Solid Electrolyte Li_6.25Al_0.25La₃Zr₂O₁₂