A bird's-eye view of Li-stuffed garnet-type Li7La3Zr2O12 ceramic electrolytes for advanced all-solid-state Li batteries

Samson, Alfred Junio; Hofstetter, Kyle; Bag, Sourav; Thangadurai, Venkataraman

doi:10.1039/c9ee01548e

Cited by 401 publications

(337 citation statements)

References 208 publications

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“…[40] In the case of the doped LLZO films, two different regimes appear. At lower temperatures there is a difference in E a of about 0.1 eV (0.38(1) eV in the Ga-LLZO film and 0.49(4) eV in the Al-LLZO film), a difference that is in good agreement with the results for sintered pellets of Rettenwander et al [37] This difference disappears in the hightemperature regime (above 100 °C), in which the E a of both doped LLZO films converges to 0.32 (3) eV. This non-Arrhenius behavior was previously observed in the Ga-doped films investigated by Rawlence et al [18] Cuervo-Reyes et al attributed this bending to ion-ion correlation effects at higher temperatures.…”

Section: Ionic and Electronic Conductivitysupporting

confidence: 84%

“…[16] Still, this is not enough to match the resistances of state-of-the-art liquid electrolytes. According to estimations by Samson et al, [3] submicron films with an ionic conductivity above 0.1 mS cm -1 are necessary to be on a par with standard liquid electrolytes. Yi et al have been able to measure conductivities above 0.1 mS cm -1 but in sheets in the micrometer range and only after annealing at 1130 °C.…”

Section: Introductionmentioning

confidence: 99%

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Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

Sastre

Priebe

Döbeli

et al. 2020

Adv Materials Inter

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The high ionic conductivity and wide electrochemical stability of the lithium garnet Li7La3Zr2O12 (LLZO) make it a viable solid electrolyte for all‐solid‐state lithium batteries with superior capacity and power densities. Contrary to common ceramic processing routes of bulk pellets, thin film solid electrolytes could enable large‐area fabrication, and increase energy and power densities by reducing the bulkiness, weight and critically, the area‐specific resistance of the electrolyte. Fabrication of LLZO films has nonetheless been challenging because of lithium losses and formation of impurity phases that result in low densities and poor ionic conductivities as compared to bulk pellets. Here, a scalable method for fabricating submicron films of LLZO employing co‐sputtering from doped LLZO and Li2O targets is presented. A record ionic conductivity of 1.9 × 10−4 S cm–1 is measured for dense and uniform cubic‐phase Ga‐substituted LLZO films annealed at 700 °C in oxygen, which is comparable to the values in high‐temperature sintered pellets and outperforms by one order of magnitude the latest record for LLZO thin films as well as the typical conductivities in the well‐established LiPON electrolyte. This result is an important milestone to realize all‐vacuum deposited solid‐state batteries with higher power density.

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Section: Ionic and Electronic Conductivitysupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

Sastre

Priebe

Döbeli

et al. 2020

Adv Materials Inter

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“…Many SSEs have been reported, including lithium phosphorus oxynitride (LiPON) 3 , sul de-type 4 , sodium superionic conductor (NASICON)-type 5,6 , perovskite-type 7 , halide-type 8 , and garnet-type 9 . Among them, garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) is promising because of its excellent chemical/electrochemical stability with Li metal and its high ionic conductivity at room temperature 10,11 . LLZO has a high shear modulus (~55 GPa) and Li transference number (~1), and was therefore predicted to prevent Li dendrite growth based on Sand's theory [12][13][14][15] .…”

Section: Introductionmentioning

confidence: 99%

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

Huo

Gao

Zhao

et al. 2020

Preprint

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Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, a flexible electron-blocking interfacial shield (EBS) is proposed to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm-2 and stable cycling for over 400 h at 1 mA cm-2 (1 mAh cm-2) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

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“…[ 26–32 ] Among them, garnet‐type SSEs have attracted tremendous interest due to their high ionic conductivity, chemical stability, and superior stability against LMA. [ 33–38 ] Unfortunately, the garnet suffers from poor wettability with LMA that the LMA/garnet interface presents a large resistance. [ 39–42 ] To tackle this challenge, it is critical to turn the garnet from lithiophobic to lithiophilic state.…”

Section: Introductionmentioning

confidence: 99%

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

Duan

Huang

Wang

et al. 2020

Adv Funct Materials

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Scientific and technological interest in solid-state Li metal batteries (SSLMBs) arises from their excellent safety and promising high energy density. However, the practical application of SSLMBs is hindered by poor contact between the Li metal anode (LMA) and solid-state electrolytes (SSEs). To circumvent this limitation, a pattern-guided approach that shapes the LMA/SSE contact is disclosed to offer fast Li ion conduction in the interface. A thermallytreated copper foam is used as the lithophilic pattern to confine and guide Li for forming a tight contact with garnet-type SSE. The contact can be easily manipulated according to the shape of lithiophilic pattern, facilitating cell assembly. The resulting Li|patterned garnet|Li symmetric cell exhibits an interfacial resistance of 9.8 Ω cm 2 , which is dramatically lower than that of 998 Ω cm 2 for Li|pristine garnet|Li symmetric cell. Being used in Li-sulfur batteries, the patterned garnet effectively eliminates the polysulfide shuttle and enables stable cycling performance, showing a low capacity decay of 0.035% per cycle over 1000 cycles. The fundamental contact process of metallic anodes/SSEs is carefully investigated. This contact strategy provides a new design concept to improve the interface wettability via a lithiophilic pattern for a variety of SSEs that cannot wet with metallic anodes.

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A bird's-eye view of Li-stuffed garnet-type Li₇La₃Zr₂O₁₂ ceramic electrolytes for advanced all-solid-state Li batteries

Abstract: Analysed current trends in development of garnet-type structured Li7La3Zr2O12-based oxides as solid electrolytes for next-generation all-solid-state lithium batteries.

Cited by 401 publications

References 208 publications

Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

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A bird's-eye view of Li-stuffed garnet-type Li7La3Zr2O12 ceramic electrolytes for advanced all-solid-state Li batteries

Abstract: Analysed current trends in development of garnet-type structured Li7La3Zr2O12-based oxides as solid electrolytes for next-generation all-solid-state lithium batteries.

Cited by 401 publications

References 208 publications

Lithium Garnet Li7La3Zr2O12 Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

Lithium Garnet Li7La3Zr2O12 Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

Contact Info

Product

Resources

About

A bird's-eye view of Li-stuffed garnet-type Li₇La₃Zr₂O₁₂ ceramic electrolytes for advanced all-solid-state Li batteries

Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities

Lithium Garnet Li₇La₃Zr₂O₁₂ Electrolyte for All‐Solid‐State Batteries: Closing the Gap between Bulk and Thin Film Li‐Ion Conductivities