A Simple and Efficient Strategy for Ameliorating Li/LLZO Interfacial Contact

Liu, Jiawei; Guo, Weichang; Hong, Guo; Xu, Chen‐Liang; Zhang, Liang; Chen, Yifei; Shen, Fei; Han, Xiaogang

doi:10.1021/acs.energyfuels.2c01770

Cited by 17 publications

(8 citation statements)

References 26 publications

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“…Coating layers are also demonstrated to be effective ways to engineer the interface between garnet LLZO and the Li metal. Metal oxides such as Al 2 O 3 and Ga 2 O 3 layers are reported to be effective for the beneficial conversion reaction with the Li metal. Hu et al used the atom layer deposition method to deposit an ultrathin Al 2 O 3 coating on garnet-like Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 , which dramatically improved the wetting and stability of garnet SSE .…”

Section: Introductionmentioning

confidence: 99%

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

Zhang,

Guo,

Zhang

et al. 2023

Energy Fuels

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Garnet-type Li7La3Zr2O12 (LLZO) is regarded as one of the most promising solid-state electrolytes due to its good thermal stability, high mechanical strength, wide electrochemical window, and good stability against Li metal. However, Li and LLZO have poor physical contact, leading to a large interfacial resistance and poor electrochemical performance. It is recognized that LLZO is intrinsic lithiophilic. But LLZO easily reacts with H2O and CO2 in air and generates Li2CO3 and other inevitable surface contaminants. The contaminated surface results in poor interfacial wettability against Li metal. Herein, an air-stable surface layer is introduced to Li6.4La3Zr1.4Ta0.6O12 (LLZTO) by simply reacting LLZTO with a LiPF6-based liquid electrolyte. During the reacting process, Li2CO3 is removed and a lithiophilic and ion-conductive modified layer is formed. The layer helps to build a uniform and intimate contact between Li and LLZTO. The interfacial resistance is reduced to 15.675 Ω cm2, less than one fifth of that between bare LLZTO and Li. Benefiting from the favorable interface, stable Li plating and stripping can be conducted for over 1000 h at a current density of 0.22 mA cm–2. Even after being exposed to air for 3 days, the interfacial resistance of surface-modified LLZTO against Li remains as low as 36.29 Ω cm2 and performs stable Li plating and stripping for 1000 h. Moreover, the quasi-solid-state Li metal batteries of Li/LLZTO/LiCoO2, Li/LLZTO/LiNi0.8Co0.1Mn0.1O2, and Li/LLZTO/LiNi0.5Mn1.5O4 exhibit excellent cycling performances, which confirms the feasibility of the strategy in the practical manufacture.

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Section: Introductionmentioning

confidence: 99%

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

Zhang,

Guo,

Zhang

et al. 2023

Energy Fuels

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“…This layer protects the LLZO sample from the formation of Li 2 CO 3 on the surface. Along with that it also reduces the interfacial resistance from 1789 Ω/cm 2 to 4.35Ω/cm 2 with an ionic conductivity of 7.0 × 10 –4 S cm –1 …”

Section: Methods and Techniques To Improve Stability Of Garnet Type L...mentioning

confidence: 99%

“…It can enhance ionic conductivity, improve stability, and reduce the interfacial resistance and contact angle between electrolyte and electrode. In LLZO, different dopants like Mg, Al, Si, Ca, Ti, Cr, Fe, Ga, Rb, Sr, Y, Nb, Mo, In, Sb, Te, Ba, Ce, Gd, Ta, and W − have been used. These dopants and their respective sites have been chosen considering their ionic radii and coordination number to improve the phase stability.…”

Section: Elements Dopingmentioning

confidence: 99%

Review on Impurity and Conductivity Issues of Garnet Type Li₇La₃Zr₂O₁₂: Mechanisms, Solutions, and Perspectives

Alam,

Das

2023

Energy Fuels

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Garnet-type solid-state electrolyte Li7La3Zr2O12 (LLZO) is the most suitable choice for an all-solid-state battery (ASSB) electrolyte. However, upon air/moisture exposure LLZO sufferers problems like surface contamination and poor ionic conductivity. This eventually leads to issues like (a) sample degradation, (b) high interfacial resistance, (c) low voltage window, (d) reduced capacity and energy density, (e) poor power density and rate performance, and limited cycle life. In the present work, we have critically reviewed recent research progress on (i) the surface contamination removal process and (ii) the doping effect in pristine garnet ceramics. This review mainly focuses on the changes in electrical properties of surface-treated and untreated LLZO. Finally, a comparative study describes the best practices to avoid surface contamination and improve conductivity.

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“…In contrast, Ga-0.142-LLZO exhibits improved Li wettability, suggesting that Ga precipitation is beneficial for Li wettability. The following reactions may occur at the interface between the molten Li and the LLZO pellet surface [47]:…”

Section: Effect Of Ga Precipitation On the Electrochemicalmentioning

confidence: 99%

Stabilization of Li7La3Zr2O12 Solid Electrolyte through Ga-Based Precipitates and the Ga–Au Surface Layer

Kim,

Nguyen,

Chun

et al. 2024

International Journal of Energy Research

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Garnet-type Li7La3Zr2O12 (LLZO) is a promising oxide solid electrolyte with high ionic conductivity and excellent stability toward Li metal. However, the presence of grain boundaries (GBs) causes a decrease in the ionic conductivity and cycling stability of the sintered LLZO. Herein, we promote the Ga precipitation at GBs through excessive doping with Ga/Al/Ta, simultaneously depositing a few nanometers thickness Au layer to form a Ga–Au surface layer. High-temperature sintering of heavily doped LLZO induces Ga precipitation, effectively filling the GB of the pellet. Consequently, the relative density and ionic conductivity are increased. Furthermore, nanoscale Au encounters precipitated Ga and forms a new Ga–Au layer, which reduces the contact resistance. The new layer prevents direct contact between molten Li and Ga-based composites at the GBs, thus enhancing the cycling stability. Therefore, it demonstrates the synergistic effect that the precipitated Ga improves the compactness of the LLZO electrolyte, whereas the Ga–Au layer enhances the cycling stability. It provides a straightforward approach to address the issues originated from GBs and increase the cycling stability of LLZO, thereby contributing to the practical application of all-solid-state batteries.

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A Simple and Efficient Strategy for Ameliorating Li/LLZO Interfacial Contact

Cited by 17 publications

References 26 publications

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

Review on Impurity and Conductivity Issues of Garnet Type Li₇La₃Zr₂O₁₂: Mechanisms, Solutions, and Perspectives

Stabilization of Li7La3Zr2O12 Solid Electrolyte through Ga-Based Precipitates and the Ga–Au Surface Layer

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A Simple and Efficient Strategy for Ameliorating Li/LLZO Interfacial Contact

Cited by 17 publications

References 26 publications

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

In Situ Formed Surface Layer to Improve the Air Stability of LLZTO and Its Contact with the Li Metal

Review on Impurity and Conductivity Issues of Garnet Type Li7La3Zr2O12: Mechanisms, Solutions, and Perspectives

Stabilization of Li7La3Zr2O12 Solid Electrolyte through Ga-Based Precipitates and the Ga–Au Surface Layer

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Product

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About

Review on Impurity and Conductivity Issues of Garnet Type Li₇La₃Zr₂O₁₂: Mechanisms, Solutions, and Perspectives