Controlled electrochemical growth of silver microwires

Rohnke, Marcus; Best, Timo; Janek, Jürgen

doi:10.1007/s10008-004-0619-5

Cited by 19 publications

(11 citation statements)

References 12 publications

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“…Recently, Janek and co-workers reported the formation of whisker-like Li morphologies and indicated a promotion by screw dislocations that enable very high rates of several hundred mA cm −2 avoiding Li penetration 28 . These findings are backed by earlier studies on dislocation-related whisker growth in AgBr 31 . Hence, compact whisker electrodes could be the potential key for high-rate-capable lithium-metal anodes 28 .…”

Section: Introductionsupporting

confidence: 74%

Dislocations in ceramic electrolytes for solid-state Li batteries

Porz

Knez

Scherer

et al. 2021

Sci Rep

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High power solid-state Li batteries (SSLB) are hindered by the formation of dendrite-like structures at high current rates. Hence, new design principles are needed to overcome this limitation. By introducing dislocations, we aim to tailor mechanical properties in order to withstand the mechanical stress leading to Li penetration and resulting in a short circuit by a crack-opening mechanism. Such defect engineering, furthermore, appears to enable whisker-like Li metal electrodes for high-rate Li plating. To reach these goals, the challenge of introducing dislocations into ceramic electrolytes needs to be addressed which requires to establish fundamental understanding of the mechanics of dislocations in the particular ceramics. Here we evaluate uniaxial deformation at elevated temperatures as one possible approach to introduce dislocations. By using hot-pressed pellets and single crystals grown by Czochralski method of Li6.4La3Zr1.4Ta0.6O12 garnets as a model system the plastic deformation by more than 10% is demonstrated. While conclusions on the predominating deformation mechanism remain challenging, analysis of activation energy, activation volume, diffusion creep, and the defect structure potentially point to a deformation mechanism involving dislocations. These parameters allow identification of a process window and are a key step on the road of making dislocations available as a design element for SSLB.

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Section: Introductionsupporting

confidence: 74%

Dislocations in ceramic electrolytes for solid-state Li batteries

Porz

Knez

Scherer

et al. 2021

Sci Rep

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“…On SEs, their growth process occurs exclusively at the interface of the whisker with the SE and thus leads to growth away from the positive electrode. 64 On crystalline lithium-ion-conducting SEs, lithium-metal whiskers have not yet been explicitly reported, but needle-or whisker-like deposits, as well as Li nanowires with a diameter of few hundred nanometers, have already been mentioned in studies of LiPON. 39,42 In comparison, cathodic silver whisker growth on SEs has been comprehensively studied, and high exchange current densities in the order of several 100 mA$cm À2 at T = 300 C were determined during cathodic whisker growth.…”

Section: Ex Situ Scanning Electron Microscopy Of the Lithium Depositionmentioning

confidence: 99%

“…39,42 In comparison, cathodic silver whisker growth on SEs has been comprehensively studied, and high exchange current densities in the order of several 100 mA$cm À2 at T = 300 C were determined during cathodic whisker growth. 64,65 It is assumed that whiskers form at points where screw dislocations intersect the surface of the SE, but the structural prerequisites for their formation have not yet been sufficiently clarified.…”

Section: Ex Situ Scanning Electron Microscopy Of the Lithium Depositionmentioning

confidence: 99%

Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes

Krauskopf

Dippel

Hartmann

et al. 2019

Joule

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Li 7 La 3 Zr 2 O 12 (LLZO)-based garnet materials are recently being investigated as suitable electrolytes for solid-state batteries with lithium-metal electrodes. Unfortunately, lithium-metal penetration through polycrystalline garnet-type electrolytes limits the electric current density during cell charging. In this study, we introduce an electrochemical operando approach that is well suited to get insights into the early stage of lithium-metal penetration that was yet only accessible with very elaborate neutron measurements. Combined with in situ as well as ex situ electron microscopic techniques, we investigate the morphological instability of the lithium-metal anode on garnet-type solid electrolytes under cathodic load and demonstrate the inter-relationship between microkinetic aspects and lithium-penetration susceptibility.

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“…This is in stark contrast to silver whiskers, which can be fully reversibly dissolved after deposition. [50,62] One explanation for the different behavior may also be attributed to the so-called "memory effect" of electroplated metals. [63][64][65][66] While this effect was shown to facilitate the electrodissolution of freshly deposited silver metal, it was not observed for the lithium microelectrodes in this work.…”

Section: Li|llzo Electrodissolution 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

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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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Controlled electrochemical growth of silver microwires

Cited by 19 publications

References 12 publications

Dislocations in ceramic electrolytes for solid-state Li batteries

Dislocations in ceramic electrolytes for solid-state Li batteries

Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes

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

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Controlled electrochemical growth of silver microwires

Cited by 19 publications

References 12 publications

Dislocations in ceramic electrolytes for solid-state Li batteries

Dislocations in ceramic electrolytes for solid-state Li batteries

Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes

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

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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