Blocking lithium dendrite growth in solid-state batteries with an ultrathin amorphous Li-La-Zr-O solid electrolyte

Abstract Lithium metal dendrites have become a roadblock in the realization of next-generation solid-state batteries with lithium metal as high-capacity anode. The presence of surface and bulk inhomogeneities with non-negligible electronic conductivity in crystalline electrolytes such as the lithium garnet Li7La3Zr2O12 (LLZO) facilitates the growth of lithium filaments, posing a critical safety risk. Here we explore the amorphous phase of LLZO (aLLZO) as a lithium dendrite shield owing to its grain-boundary-free microstructure, stability against metallic lithium, and high electronic insulation. We demonstrate that by tuning the lithium stoichiometry in sputtered aLLZO films, the ionic conductivity can be increased up to 10-7 S cm-1 while retaining an ultralow electronic conductivity of 10-14 S cm-1. In Li/aLLZO/Li symmetric cells, plating-stripping results in no degradation of the films and current densities up to 3.2 mA cm-2 can be applied with no signs of lithium penetration. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. Finally, we demonstrate that the application of aLLZO as a coating on crystalline LLZO lowers the interface resistance and significantly impedes the formation of lithium dendrites, increasing the critical current density of a symmetric cell up to 1.3 mA cm-2 at room temperature and without external pressure. The effectiveness of the amorphous Li-La-Zr-O as lithium dendrite blocking layer can accelerate the development of more powerful and safer solid-state batteries.

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Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

10.26434/chemrxiv.13331084.v2 ◽

2021 ◽

Author(s):

Jordi Sastre ◽

Moritz H. Futscher ◽

Lea Pompizi ◽

Abdessalem Aribia ◽

Agnieszka Priebe ◽

...

Keyword(s):

Solid State ◽

Electronic Conductivity ◽

High Capacity ◽

External Pressure ◽

Lithium Metal ◽

Metallic Lithium ◽

Lithium Dendrites ◽

Lithium Garnet ◽

Solid State Batteries ◽

Lithium Dendrite

Lithium metal dendrites have become a roadblock in the realization of next-generation solid-state batteries with lithium metal as high-capacity anode. The presence of surface and bulk inhomogeneities with non-negligible electronic conductivity in crystalline electrolytes such as the lithium garnet Li7La3Zr2O12 (LLZO) facilitates the growth of lithium filaments, posing a critical safety risk. Here we explore the amorphous phase of LLZO (aLLZO) as a lithium dendrite shield owing to its grain-boundary-free microstructure, stability against metallic lithium, and high electronic insulation. We demonstrate that by tuning the lithium stoichiometry in sputtered aLLZO films, the ionic conductivity can be increased up to 10-7 S cm-1 while retaining an ultralow electronic conductivity of 10-14 S cm-1. In Li/aLLZO/Li symmetric cells, plating-stripping results in no degradation of the films and current densities up to 3.2 mA cm-2 can be applied with no signs of lithium penetration. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. Finally, we demonstrate that the application of aLLZO as a coating on crystalline LLZO lowers the interface resistance and significantly impedes the formation of lithium dendrites, increasing the critical current density of a symmetric cell up to 1.3 mA cm-2 at room temperature and without external pressure. The effectiveness of the amorphous Li-La-Zr-O as lithium dendrite blocking layer can accelerate the development of more powerful and safer solid-state batteries.<div></div>

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Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

10.26434/chemrxiv.13331084.v1 ◽

2020 ◽

Author(s):

Jordi Sastre ◽

Moritz H. Futscher ◽

Lea Pompizi ◽

Abdessalem Aribia ◽

Agnieszka Priebe ◽

...

Keyword(s):

Solid State ◽

Electronic Conductivity ◽

High Capacity ◽

Dendrite Growth ◽

Potential Candidate ◽

Sputtering Deposition ◽

Lithium Garnet ◽

Solid State Batteries ◽

Current Densities ◽

Lithium Dendrite

Lithium garnet Li7La3Zr2O12 (LLZO) electrolyte is a potential candidate for the development of solid-state batteries with lithium metal as high-capacity anode. But ceramic LLZO in the form of pellets or polycrystalline films can still suffer from lithium dendrite penetration because of surface and bulk inhomogeneities and grain boundaries with non-negligible electronic conductivity. In contrast, the amorphous phase of LLZO (aLLZO) possesses a grain-boundary-free microstructure with moderate ionic conductivity (10-7 S cm-1) and high electronic insulation (10-14 S cm-1), which in the form of thin coatings can offer resistance to lithium dendrite growth. We explore the electrochemical properties and applications of aLLZO ultrathin films prepared by sputtering deposition. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. In Li/aLLZO/Li symmetric cells, plating-stripping at current densities up to 3.2 mA cm-2 shows no signs of lithium penetration. Finally, we show that the application of aLLZO as a coating on LLZO ceramic pellets significantly impedes the formation of Li dendrites.

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Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

10.26434/chemrxiv.13331084 ◽

2020 ◽

Author(s):

Jordi Sastre ◽

Moritz H. Futscher ◽

Lea Pompizi ◽

Abdessalem Aribia ◽

Agnieszka Priebe ◽

...

Keyword(s):

Solid State ◽

Electronic Conductivity ◽

High Capacity ◽

Dendrite Growth ◽

Potential Candidate ◽

Sputtering Deposition ◽

Lithium Garnet ◽

Solid State Batteries ◽

Current Densities ◽

Lithium Dendrite

Lithium garnet Li7La3Zr2O12 (LLZO) electrolyte is a potential candidate for the development of solid-state batteries with lithium metal as high-capacity anode. But ceramic LLZO in the form of pellets or polycrystalline films can still suffer from lithium dendrite penetration because of surface and bulk inhomogeneities and grain boundaries with non-negligible electronic conductivity. In contrast, the amorphous phase of LLZO (aLLZO) possesses a grain-boundary-free microstructure with moderate ionic conductivity (10-7 S cm-1) and high electronic insulation (10-14 S cm-1), which in the form of thin coatings can offer resistance to lithium dendrite growth. We explore the electrochemical properties and applications of aLLZO ultrathin films prepared by sputtering deposition. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. In Li/aLLZO/Li symmetric cells, plating-stripping at current densities up to 3.2 mA cm-2 shows no signs of lithium penetration. Finally, we show that the application of aLLZO as a coating on LLZO ceramic pellets significantly impedes the formation of Li dendrites.

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Study on Li0.33La0.55TiO3 Solid Electrolyte with High Ionic Conductivity and Its Application in Flexible All Solid-State Battery

Nanoscale ◽

10.1039/d1nr02427b ◽

2021 ◽

Author(s):

Feihu Tan ◽

Hua An ◽

Ning Li ◽

Jun Du ◽

Zhengchun Peng

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Solid Electrolyte ◽

High Ionic Conductivity ◽

Energy Sources ◽

Solid State Battery ◽

Solid State Batteries ◽

All Solid State Batteries

As flexible all-solid-state batteries are highly safe and lightweight, they can be considered as candidates for wearable energy sources. However, their performance needs to be first improved, which can be...

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Hydrated Alkali-B11H14 Salts as Potential Solid-State Electrolytes†

Journal of Materials Chemistry A ◽

10.1039/d1ta01551f ◽

2021 ◽

Author(s):

Diego Holanda Pereira de Souza ◽

Kasper T. Møller ◽

Stephen A. Moggach ◽

Terry D Humphries ◽

Anita D’Angelo ◽

...

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Solid Electrolyte ◽

High Ionic Conductivity ◽

Solid State Batteries ◽

All Solid State Batteries ◽

Solid State Electrolytes

Metal boron-hydrogen compounds are considered as promising solid electrolyte candidates for the development of all-solid-state batteries (ASSB), owing to the high ionic conductivity exhibited by closo- and nido-boranes. In this...

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High-performance polymeric ionic liquid–silica hybrid ionogel electrolytes for lithium metal batteries

Journal of Materials Chemistry A ◽

10.1039/c6ta04767j ◽

2016 ◽

Vol 4 (36) ◽

pp. 13822-13829 ◽

Cited By ~ 33

Author(s):

Xiaowei Li ◽

Sijian Li ◽

Zhengxi Zhang ◽

Jun Huang ◽

Li Yang ◽

...

Keyword(s):

Ionic Liquid ◽

Solid State ◽

High Performance ◽

High Capacity ◽

Electrochemical Stability ◽

Rate Performance ◽

Lithium Metal ◽

Polymeric Ionic Liquid ◽

Lithium Metal Batteries ◽

Silica Hybrid

Hybrid ionogel electrolytes have high thermal and electrochemical stability, good ionic conductivity, and potential to suppress Li dendrite formation. Solid-state lithium metal batteries with hybrid electrolytes reveal high capacity and remarkable rate performance.

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Creep and Anisotropy of Free-Standing Lithium Metal Foils in an Industrial Dry Room

Journal of Electrochemical Energy Conversion and Storage ◽

10.1115/1.4052043 ◽

2021 ◽

pp. 1-32

Author(s):

Lara Dienemann ◽

Anil Saigal ◽

Michael A Zimmerman

Keyword(s):

Mechanical Properties ◽

Solid State ◽

High Volume ◽

Dominant Mode ◽

Lithium Metal ◽

Free Standing ◽

Metal Anode ◽

Lithium Metal Batteries ◽

Lithium Metal Anode ◽

Solid State Batteries

Abstract Commercialization of energy-dense lithium metal batteries relies on stable and uniform plating and stripping on the lithium metal anode. In electrochemical-mechanical modeling of solid-state batteries, there is a lack of consideration of specific mechanical properties of battery-grade lithium metal. Defining these characteristics is crucial for understanding how lithium ions plate on the lithium metal anode, how plating and stripping affect deformation of the anode and its interfacing material, and whether dendrites are suppressed. Recent experiments show that the dominant mode of deformation of lithium metal is creep. This study measures the time and temperature dependent mechanics of two thicknesses of commercial lithium anodes inside an industrial dry room, where battery cells are manufactured at high volume. Furthermore, a directional study examines the anisotropic microstructure of 100 µm thick lithium anodes and its effect on bulk creep mechanics. It is shown that these lithium anodes undergo plastic creep as soon as a coin cell is manufactured at a pressure of 0.30 MPa, and achieving thinner lithium foils, a critical goal for solid-state lithium batteries, is correlated to anisotropy in both lithium's microstructure and mechanical properties.

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Understanding the lithium dendrites growth in garnet-based solid-state lithium metal batteries

Journal of Power Sources ◽

10.1016/j.jpowsour.2021.230921 ◽

2022 ◽

Vol 521 ◽

pp. 230921

Author(s):

Yuncai Chen ◽

Yidong Jiang ◽

Shang-Sen Chi ◽

Haw Jiunn Woo ◽

Kai Yu ◽

...

Keyword(s):

Solid State ◽

Lithium Metal ◽

Lithium Metal Batteries ◽

Lithium Dendrites ◽

Dendrites Growth

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Elastic-Viscoplastic Mechanics of Lithium in a Standard Dry Room

Volume 3: Advanced Materials: Design, Processing, Characterization, and Applications ◽

10.1115/imece2020-23894 ◽

2020 ◽

Author(s):

Lara L. Dienemann ◽

Anil Saigal ◽

Michael A. Zimmerman

Keyword(s):

High Volume ◽

Lattice Diffusion ◽

Mechanical Parameters ◽

Mechanical Modeling ◽

Lithium Metal ◽

Temperature Dependent ◽

Linear Elastic ◽

Battery Safety ◽

Lithium Dendrites ◽

Solid State Batteries

Abstract In electrochemical-mechanical modeling of solid-state batteries, there is a lack of understanding of the mechanical parameters and mode of deformation of lithium metal. Understanding these characteristics is crucial for predicting the propagation of lithium dendrites through the electrolyte — a key element of battery safety. Past theories have assumed linear elastic as well as elastic-plastic deformation of lithium. However, recent experiments show that the primary mode of deformation is creep. This study replicates the temperature dependent mechanical experiments but inside an industrial dry room, where battery cells are manufactured at high volume. Furthermore, this work conducts time dependent studies — also inside the dry room — to gain insight of the large deformation theories of lithium metal. The results confirm the activation energy, which dictates the creep mechanism, is correlated to core diffusion rather than lattice diffusion.

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