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

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 Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (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<sup>-7</sup> S cm<sup>-1</sup>) and high electronic insulation (10<sup>-14</sup> S cm<sup>-1</sup>), 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<sup>-2</sup> for over 500 cycles. In Li/aLLZO/Li symmetric cells, plating-stripping at current densities up to 3.2 mA cm<sup>-2</sup> 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.

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

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 Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (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<sup>-7</sup> S cm<sup>-1</sup>) and high electronic insulation (10<sup>-14</sup> S cm<sup>-1</sup>), 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<sup>-2</sup> for over 500 cycles. In Li/aLLZO/Li symmetric cells, plating-stripping at current densities up to 3.2 mA cm<sup>-2</sup> 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.

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

2021 ◽  
Author(s):  
Jordi Sastre ◽  
Moritz 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

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.

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

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 Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (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<sup>-7</sup> S cm<sup>-1</sup> while retaining an ultralow electronic conductivity of 10<sup>-14</sup> S cm<sup>-1</sup>. In Li/aLLZO/Li symmetric cells, plating-stripping results in no degradation of the films and current densities up to 3.2 mA cm<sup>-2</sup> 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<sup>-2</sup> 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<sup>-2</sup> 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>

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

2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Jordi Sastre ◽  
Moritz H. Futscher ◽  
Lea Pompizi ◽  
Abdessalem Aribia ◽  
Agnieszka Priebe ◽  
...  
Keyword(s):  
Solid State ◽  
Ionic Conductivity ◽  
Electronic Conductivity ◽  
High Capacity ◽  
Blocking Layer ◽  
Lithium Metal ◽  
Microstructure Stability ◽  
Lithium Dendrites ◽  
Solid State Batteries ◽  
Lithium Dendrite

AbstractLithium dendrites have become a roadblock in the realization of solid-state batteries with lithium metal as high-capacity anode. The presence of surface and bulk defects in crystalline electrolytes such as the garnet Li7La3Zr2O12 (LLZO) facilitates the growth of these hazardous lithium filaments. Here we explore the amorphous phase of LLZO as a lithium dendrite shield owing to its grain-boundary-free microstructure, stability against lithium metal, and high electronic insulation. By tuning the lithium stoichiometry, the ionic conductivity can be increased by 4 orders of magnitude while retaining a negligible electronic conductivity. In symmetric cells, plating-stripping shows no signs of lithium penetration up to 3.2 mA cm−2. The dense conformal nature of the films enables microbatteries with an electrolyte thickness of only 70 nm, which can be cycled at 10C for over 500 cycles. The application of this material as a coating on crystalline LLZO lowers the interface resistance and increases the critical current density. The effectiveness of the amorphous Li-La-Zr-O as dendrite blocking layer can accelerate the development of better solid-state batteries.

Low Electronic Conductivity of Li7La3Zr2O12 (LLZO) Solid Electrolytes from First Principles

2020 ◽  
Author(s):  
Alex Squires ◽  
Daniel Davies ◽  
Sunghyun Kim ◽  
David Scanlon ◽  
Aron Walsh ◽  
...  
Keyword(s):  
First Principles ◽  
Solid Electrolytes ◽  
Electronic Conductivity ◽  
Lithium Ion ◽  
Dendrite Growth ◽  
Operating Conditions ◽  
Electronic Conductivities ◽  
Lithium Garnet ◽  
Lithium Dendrite ◽  
Lithium Garnets

Lithium-rich garnets such as Li7 La3 Zr2 O12 (LLZO) are promising solid electrolytes with potential applications in all–solid-state lithium-ion batteries. The practical use of lithium-garnet electrolytes is currently limited by pervasive lithium-dendrite growth during battery cycling, which leads to short-circuiting and cell failure. One proposed mechanism for dendrite growth is the reduction of lithium ions to lithium metal within the electrolyte. Lithium garnets have been proposed to be susceptible to this growth mechanism due to high electronic conductivities [Han et al. Nature Ener. 4 187, 2019]. The electronic conductivities of LLZO and other lithium-garnet solid electrolytes, however, are not yet well characterised. Here, we present a general scheme for calculating the intrinsic electronic conductivity of a nominally-insulating material under variable synthesis and operating conditions from first principles, and apply this to the prototypical lithium-garnet LLZO. Our model predicts that under typical battery operating conditions, electron and hole carrier-concentrations in bulk LLZO are negligible, irrespective of initial synthesis conditions, and electron and hole mobilities are low (<1 cm2 V−1 s−1 ). These results suggest that the bulk electronic conductivity of LLZO is not sufficiently high to cause bulk lithium-dendrite formation during cell operation. Any non-negligible electronic conductivity in lithium garnets is therefore likely due to extended defects or surface contributions.

Low Electronic Conductivity of Li7La3Zr2O12 (LLZO) Solid Electrolytes from First Principles

2020 ◽  
Author(s):  
Alex Squires ◽  
Daniel Davies ◽  
Sunghyun Kim ◽  
David Scanlon ◽  
Aron Walsh ◽  
...  
Keyword(s):  
First Principles ◽  
Solid Electrolytes ◽  
Electronic Conductivity ◽  
Lithium Ion ◽  
Dendrite Growth ◽  
Operating Conditions ◽  
Electronic Conductivities ◽  
Lithium Garnet ◽  
Lithium Dendrite ◽  
Lithium Garnets

Lithium-rich garnets such as Li7 La3 Zr2 O12 (LLZO) are promising solid electrolytes with potential applications in all–solid-state lithium-ion batteries. The practical use of lithium-garnet electrolytes is currently limited by pervasive lithium-dendrite growth during battery cycling, which leads to short-circuiting and cell failure. One proposed mechanism for dendrite growth is the reduction of lithium ions to lithium metal within the electrolyte. Lithium garnets have been proposed to be susceptible to this growth mechanism due to high electronic conductivities [Han et al. Nature Ener. 4 187, 2019]. The electronic conductivities of LLZO and other lithium-garnet solid electrolytes, however, are not yet well characterised. Here, we present a general scheme for calculating the intrinsic electronic conductivity of a nominally-insulating material under variable synthesis and operating conditions from first principles, and apply this to the prototypical lithium-garnet LLZO. Our model predicts that under typical battery operating conditions, electron and hole carrier-concentrations in bulk LLZO are negligible, irrespective of initial synthesis conditions, and electron and hole mobilities are low (<1 cm2 V−1 s−1 ). These results suggest that the bulk electronic conductivity of LLZO is not sufficiently high to cause bulk lithium-dendrite formation during cell operation. Any non-negligible electronic conductivity in lithium garnets is therefore likely due to extended defects or surface contributions.

Low resistant and stable lithium-garnet electrolyte interface enabled by a multifunctional anode additive for solid-state lithium batteries

2021 ◽  
Author(s):  
Chencheng Cao ◽  
Yijun Zhong ◽  
Kimal Chandula Wasalathilake ◽  
Moses O. Tade ◽  
Xiaomin Xu ◽  
...  
Keyword(s):  
Solid State ◽  
Energy Density ◽  
Lithium Batteries ◽  
The Core ◽  
Intrinsic Stability ◽  
Electrolyte Interface ◽  
Lithium Garnet ◽  
Solid State Batteries ◽  
Core Part

Solid-state batteries (SSBs) have attracted considerable attention due to the high intrinsic stability and theoretical energy density. As the core part, garnet electrolyte has been extensively investigated due to high...

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