Dendrite nucleation in lithium-conductive ceramics

Li, Guanchen; Monroe, Charles W.

doi:10.1039/c9cp03884a

Cited by 66 publications

(66 citation statements)

References 31 publications

(53 reference statements)

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“…22 Since we want to understand the impact of the ASR on |Dp| we calculated |Dp| for the cells studied here according to |Dp| ¼ 2pf int (63 bulk CCD) 1/2 , with 3 bulk ¼ 3 rel 3 and 3 rel z 50. 42,44 In contrast to the earlier report, the values obtained range from 5 Â 10 3 Pa to 7 Â 10 5 Pa. The signicantly higher values correspond to higher ASR values.…”

Section: Failure Mechanismmentioning

confidence: 61%

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The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

et al. 2020

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Ceramic batteries equipped with Li-metal anodes are expected to double the energy density of conventional Li-ion batteries. Besides high energy densities, also high power is needed when batteries have to be developed for electric vehicles. Practically speaking, so-called critical current densities (CCD) higher than 3 mA cm À2 are needed to realize such systems. As yet, this value has, however, not been achieved for garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) being one of the most promising ceramic electrolytes.Most likely, CCD values are influenced by the area specific resistance (ASR) governing ionic transport across the Li|electrolyte interface. Here, single crystals of LLZO with adjusted ASR are used to quantify this relationship in a systematic manner. It turned out that CCD values exponentially decrease with increasing ASR. The highest obtained CCD value was as high as 280 mA cm À2 . This value should be regarded as the room-temperature limit for LLZO when no external pressure is applied. Concluding, for polycrystalline samples either stack pressure or a significant increase of the interfacial area is needed to reach current densities equal or higher than the above-mentioned target value.

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Section: Failure Mechanismmentioning

confidence: 61%

“…In a very recent experimental paper by Li and Monroe, the authors report about the mechanism of dendrite nucleation. 42 They showed that the stress associated with dendrite growth is about 1 kPa. This value is far below the fracture stress of about |Dp| ¼ 6 MPa for LLZO.…”

Section: Failure Mechanismmentioning

confidence: 99%

The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

et al. 2020

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“…[72] A precise knowledge of the charge transfer kinetics is very important for the prediction of precise potential profiles in batteries and modeling approaches for lithium metal growth through ceramic electrolytes. [38,49,73] With this work, we hope to stimulate a rethinking of the kinetics of metal electrodes on single ion conductors and to inspire future theoretical and experimental work on the atomistic understanding of the charge transfer reaction. This understanding is required to obtain meaningful predictions of the rate capability of lithium metal anodes under ideal conditions.…”

Section: Discussionmentioning

confidence: 98%

“…For precise theoretical models dealing with the lithium metal anode in SSBs, the charge transfer reaction needs to be well known. [38] In literature, the charge transfer resistance is often set equal to the interfacial impedance. However, recent results clearly show that the Li|LLZO interfacial impedance does not reflect the charge transfer alone, but is rather dominated by current constriction resistances in the ISE at the interface.…”

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

140

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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“…For example, numerous works have reported the resistance at GB related to the decrease in the ion conductivity in LLZO, [18][19][20][21] while some other studies have observed contradictory results, where the sample with small grain size has higher conductivity than that containing large-sized grains, indicating the faster ion transport at the GBs. [22][23][24] Moreover, GBs are expected to contribute to the Li dendrite growth in LLZO, [25][26][27] which leads to the short-circuiting of the cell 22,[28][29][30][31] . It is reported that the inhomogeneous depletion 30 and low ion conductivity 32 at the GB are responsible for the dendrite growth.…”

Section: Introductionmentioning

confidence: 99%

Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte

Gao

Jalem

Tian

et al. 2021

Preprint

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For real application to the all-solid-state batteries, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the atomic-scale defect stabilities and transports of ions around the GBs is still far from understood. Here, the first-principles investigation on the promising garnet Li7La3Zr2O12 solid electrolyte GBs has been carried out. Our study reveals a GB-dependent behavior for the Li-ion transport correlated to the diffusion network. Especially, the Σ3(112) tilt GB model exhibits a quite high Li-ion conductivity comparable to that in bulk, and a fast intergranular diffusion contrary to the former concepts. Moreover, the preference of the electron accumulation at the Σ3(112) GB was uncovered in terms of the lower Li interstitial formation energies. This phenomenon is further enhanced by the presence of the Schottky-like defect, leading to the increase in the electronic conductivity at GBs, which plays a key role in the Li dendrite growth.

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Dendrite nucleation in lithium-conductive ceramics

Abstract: A chemomechanical analysis suggests that bulk lithium plating in polycrystalline LLZO becomes energetically favourable above a critical current. This grain-coating mechanism rationalizes dendrite nucleation without making reference to surface cracks.

Cited by 66 publications

References 31 publications

The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

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

Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte

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Dendrite nucleation in lithium-conductive ceramics

Abstract: A chemomechanical analysis suggests that bulk lithium plating in polycrystalline LLZO becomes energetically favourable above a critical current. This grain-coating mechanism rationalizes dendrite nucleation without making reference to surface cracks.

Cited by 66 publications

References 31 publications

The natural critical current density limit for Li7La3Zr2O12 garnets

The natural critical current density limit for Li7La3Zr2O12 garnets

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

Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte

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Product

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The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

The natural critical current density limit for Li₇La₃Zr₂O₁₂ garnets

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