Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition

Smetaczek, Stefan; Wachter-Welzl, Andreas; Wagner, Reinhard; Rettenwander, Daniel; Amthauer, Georg; Andrejs, Lukas; Taibl, Stefanie; Limbeck, Andreas; Fleig, Jürgen

doi:10.1039/c9ta00356h

Cited by 33 publications

(26 citation statements)

References 67 publications

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“…Yet, in LM-SSB research on garnet type solid electrolytes, microelectrodes are currently mainly used for local conductivity measurements on the ISE. [42,43] By performing different electrochemical methods like PEIS, cyclic voltammetry, and galvanostatic as well as potentiostatic techniques on in situ generated lithium microelectrodes, we comprehensively measure the kinetics at the Li|LLZO interface and reveal the fast intrinsic nature of the elementary charge transfer reaction.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…Throughout the literature, however, we can find a spread in the reported ionic conductivity and activation barrier values, even within the same class of materials. Whereas significant variations in the Li + ionic transport has been reported as a function of batch variation, particle size, synthesis procedure, and even due to local sample inhomogeneity, 30,31 to this day, no rigorous study on the interlaboratory reproducibility in the ionic conductivity measurement via impedance spectroscopy has been performed. Inspired by the standardization and benchmarking efforts in other communities, e.g.…”

mentioning

confidence: 99%

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

Ohno¹,

Bernges²,

Buchheim³

et al. 2020

Preprint

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Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an interlaboratory reproducibility of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm-1 in the measured total ionic conductivity (1.3 – 5.8 mScm-1 for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.

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“…[29] But Smetaczek et al claimed that neither local Al content nor local Li content had an obvious correlation with the local ionic conductivity in LALZO. [30] Maybe other factors have pronounced effects on the difference in ionic conductivity, which requires further study.…”

Section: Uncontrollable LI Dendritementioning

confidence: 99%

Interface between Lithium Metal and Garnet Electrolyte: Recent Progress and Perspective

Wang

Huang

Zhang

2020

Batteries & Supercaps

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Garnet electrolytes (GEs) with high ion conductivity, excellent stability against lithium metal (LM) as well as wide electrochemical potential window are attracting increasing interest as they have the potential to enable all-solid-state Li metal batteries (ASSLMBs). However, GEs-based ASSLMBs deeply suffer from daunting problems such as high resistance, fast short circuit, and rapid performance degradation, which can be largely attributed to unsatisfactory LM/GE interface. To this end, this minireview focuses on the LM/GE interface by summarizing the main challenges comprehensively, recapitulating emerging strategies for these challenges, and providing perspectives for future research.

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Local Li-ion conductivity changes within Al stabilized Li₇La₃Zr₂O₁₂ and their relationship to three-dimensional variations of the bulk composition

Abstract: Investigating conductivity variations in Al stabilized LLZO by combining microelectrode impedance spectroscopy with spatially resolved chemical analysis.

Cited by 33 publications

References 67 publications

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

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

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

Interface between Lithium Metal and Garnet Electrolyte: Recent Progress and Perspective

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Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition

Abstract: Investigating conductivity variations in Al stabilized LLZO by combining microelectrode impedance spectroscopy with spatially resolved chemical analysis.

Cited by 33 publications

References 67 publications

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

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

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

Interface between Lithium Metal and Garnet Electrolyte: Recent Progress and Perspective

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Local Li-ion conductivity changes within Al stabilized Li₇La₃Zr₂O₁₂ and their relationship to three-dimensional variations of the bulk composition

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

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