Structural (in)stability and spontaneous cracking of Li-La-zirconate cubic garnet upon exposure to ambient atmosphere

Kobi, Sushobhan; Mukhopadhyay, Amartya

doi:10.1016/j.jeurceramsoc.2018.06.014

Cited by 30 publications

(38 citation statements)

References 41 publications

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“…Whereas the cubic garnet structure of a dense pellet with 96% relative theoretical density was preserved after 6 weeks of exposure to 80% RH, forming a 25 µm thick Li 2 CO 3 layer followed by a reduction in ionic conductivity (6.45-3.61 × 10 −4 S cm −1 ), [232] a pellet with 83% relative density exposed to humid atmosphere (≈75%-85% RH) spontaneously cracked and was pulverized after merely 3 weeks of exposure, mainly due to the formation of the pyrochlore phase La 2 Zr 2 O 7 . [233] As such, the introduction of a sintering agent (Al 2 O 3 , Y 2 O 3 ) can greatly reduce the susceptibility of LLZO to moisture and CO 2 by increasing the relative density. [231,246] Recently, the microstructure of air-sintered LLZO was modified by controlling the powder size and eliminating powder agglomeration with freeze drying, achieving 98% relative theoretical density in addition to abnormal grain growth (≈460 µm) and minimal grain boundaries.…”

Section: Oxidementioning

confidence: 99%

“…The stability of solid electrolytes in ambient air is imperative for ease of preparation during manufacturing and the cellassembly process to reduce production costs. Moreover, poor air stability can lead to chemical [136,[229][230][231] and mechanical degradation, [232,233] resulting in a decrease of ionic conductivity, high interfacial resistances, and limited electrochemical device performance. [230,234]…”

Section: Chemical Stability In Ambient Air and Its Effect On Electrolyte Performancementioning

confidence: 99%

“…[235,240,242,243] For the preferable fast conducting cubic Li 7 La 3 Zr 2 O 12 , a spontaneous and rapidly reversible Li + /H + exchange in water was observed without structure degradation, confirmed by a decrease in the lattice parameter due to the partial Li + /H + exchange while the original cubic 3 Ia d structure was preserved. [235,240] After the Li + /H + ion exchange upon exposure to aqueous solutions was observed in lithium-garnet-type powders, the effect of air exposure (mainly moisture and CO 2 ) was investigated for dense Li 7 La 3 Zr 2 O 12 [231] and Al-, [136,229,230,233] Ta-, [232] Ga-, [244] Nb-, [245] and Nb/Y [246] -doped LLZO pellets. The garnettype LLZO structure is thermodynamically unstable when exposed to ambient (dry to humid) air, leading to the formation of a lithium carbonate (Li 2 CO 3 ) contamination layer and higher interfacial resistance at the Li/LLZO interface.…”

Section: Oxidementioning

confidence: 99%

“…After the Li + /H + ion exchange upon exposure to aqueous solutions was observed in lithium‐garnet‐type powders, the effect of air exposure (mainly moisture and CO 2 ) was investigated for dense Li 7 La 3 Zr 2 O 12 [ 231 ] and Al‐, [ 136,229,230,233 ] Ta‐, [ 232 ] Ga‐, [ 244 ] Nb‐, [ 245 ] and Nb/Y [ 246 ] ‐doped LLZO pellets. The garnet‐type LLZO structure is thermodynamically unstable when exposed to ambient (dry to humid) air, leading to the formation of a lithium carbonate (Li 2 CO 3 ) contamination layer and higher interfacial resistance at the Li/LLZO interface.…”

Section: Solid Electrolytes: Sulfides and Oxidesmentioning

confidence: 99%

See 3 more Smart Citations

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Kim

Balaish

Wadaguchi

et al. 2020

Advanced Energy Materials

398

355

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lightweight, and compact and allow for versatile device geometries. They must also be scalable and offer high energy density to provide improved packing efficiency and longer device operation. Although both Ni-MH batteries and LIBs have been commercialized since the 1990s, [1] LIBs possess twice the gravimetric/volumetric energy density (250 Wh kg −1 /700 Wh L −1 vs 170 Wh kg −1 /350 Wh L −1 ), [2] higher battery voltage (3.7 V vs 1.2 V), and longer cycle life with lower self-discharge, [3] contributing tremendously to the proliferation of portable electronic devices (e.g., mobile phones, laptops, cameras, tablets) as well as emerging new technologies such as wearable electronic devices (e.g., smart watches and sport-related tracking devices). Their high gravimetric/ volumetric energy density, [2] excellent cycle life (thousands of cycles), and lack of the memory effect have positioned LIBs as state-of-the-art power sources and one of the greatest successes of modern electrochemistry, revolutionizing the way we acquire, process, transmit, and share information globally. Nevertheless, advances in battery energy density, safety, costs, and flexibility in shape and size are still needed to keep up with the rapidly growing demand for devices with even longer runtime as well as real-time data collection and transmission capabilities in addition to increasingly energy-demanding applications such as electric vehicles (EVs) and electricity grid storage. Even though LIBs were first commercialized in all electric vehicles (EVs) in 2010 and also emerged for grid application in the same time frame, the low energy density (≈250 Wh kg −1 ) and high average cost (≈$156 kWh −1 in 2019) of conventional LIBs do not meet the requirements for advanced EVs and grid-scale energy storage. [4][5][6] Specifically, the driving range per charge (miles), which is related to the energy density of each cell, and the cost are important parameters for EVs. For example, one 85 kWh battery pack in a Tesla Model S requires 7104 LIB cells, with an energy density of 265 Wh kg −1 , providing an average range of 250 miles, which is ahead of the range of other EVs but still behind the target of 375 miles. [4] In grid-scale applications, LIBs can be used for various tasks: frequency regulation, peak shaving, load leveling, and large-scale integration of renewable energies, with specific properties generally required for each task. For frequency regulation, LIBs need to provide a fast response, high rate performance, and high-power capability,The introduction of new, safe, and reliable solid-electrolyte chemistries and technologies can potentially overcome the challenges facing their liquid counterparts while widening the breadth of possible applications. Through tech-historic evolution and rationally analyzing the transition from liquidbased Li-ion batteries (LIBs) to all-solid-state Li-metal batteries (ASSLBs), a roadmap for the development of a successful oxide and sulfide-based ASSLB focusing on interfacial challenges is introduced, while accounting ...

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Section: Oxidementioning

confidence: 99%

Section: Chemical Stability In Ambient Air and Its Effect On Electrolyte Performancementioning

confidence: 99%

Section: Oxidementioning

confidence: 99%

Section: Solid Electrolytes: Sulfides and Oxidesmentioning

confidence: 99%

See 2 more Smart Citations

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Kim

Balaish

Wadaguchi

et al. 2020

Advanced Energy Materials

398

355

View full text Add to dashboard Cite

show abstract

“…The contaminating layer formed on the surface of LLZO decreases the ionic conductivity and induces an increase of interfacial resistance of the electrolyteelectrode interface. Studies from Kobi and Mukhopadhyay described that spontaneous cracking of LLZO occurs during storage of c-LLZO pellets in ambient air atmosphere for a few weeks possibly due to the formation of La 2 Zr 2 O 7 in the LLZO bulk [87]. X-ray diffraction studies indicate the formation of Li 2 CO 3 and LaAlO 3 just the 3rd day ahead upon exposure to air following by the formation of La 2 Zr 2 O 7 .…”

Section: Challenges On Llzo Air Stabilitymentioning

confidence: 99%

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

et al. 2021

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All-solid-state lithium batteries (ASSLBs), which use solid electrolytes instead of liquid ones, have become a hot research topic due to their high energy and power density, ability to solve battery safety issues, and capabilities to fulfill the increasing demand for energy storage in electric vehicles and smart grid applications. Garnet-type solid electrolytes have attracted considerable interest as they meet all the properties of an ideal solid electrolyte for ASSLBs. The garnet-type Li7La3Zr2O12 (LLZO) has excellent environmental stability; experiments and computational analyses showed that this solid electrolyte has a high lithium (Li) ionic conductivity (10−4–10−3 S·cm−1), an electrochemical window as wide as 6 V, stability against Li metal anode, and compatibility with most of the cathode materials. In this review, we present the fundamentals of garnet-type solid electrolytes, preparation methods, air stability, some strategies for improving the conductivity based on experimental and computational results, interfacial issues, and finally applications and challenges for future developments of LLZO solid electrolytes for ASSLBs.

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A Comparative Study of Polycrystal/Single‐Crystal LiNi_0.8Co_0.1Mn_0.1O₂ in All‐Solid‐State Li‐Ion Batteries with Halide‐Based Electrolyte under Low Stacking Pressure

et al. 2023

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Composite cathodes consisting of a LiNi0.8Co0.1Mn0.1O2 (NCM) cathode and brittle Li3InCl6 (LIC) solid‐state electrolyte (SSE) are assessed for all‐solid‐state Li‐ion battery (ASSLIB) applications under a low stacking pressure (coin‐cell configuration: ≈2.0 MPa). Herein, an investigation is conducted to understand how the internal particle morphologies of the polycrystal (PC‐)/single‐crystal (SC‐) NCM cathode materials affect the internal cracking within the composite electrodes and thereby electrode performance. Extensive debonding between NCM and LIC takes place even at a very low current density (0.03C) with high voltage (4.4 V), but substantially narrower/shorter debonding gaps are observed for SC‐NCM as compared with PC‐NCM (wider/lengthier) due to their different particle sizes. High current rates (e.g., 0.1C) bring about greater strain rates in PC‐NCM particles, resulting in widespread microcracking along the grain boundaries between primary particles and consequently creating “dead zones” that are isolated from the ionic and electronic conduction pathways. Although SC‐NCM shows microcracking within the agglomerates, individual NCM crystals remain in close contact with the SSEs because of noticeably fewer grains in the agglomerations than in the PC‐NCM secondary particles. A low‐pressure SC‐NCM ASSLIB is demonstrated with good cycle stability comparable with that of a liquid‐electrolyte cell even under stressful currents.

show abstract

Structural (in)stability and spontaneous cracking of Li-La-zirconate cubic garnet upon exposure to ambient atmosphere

Cited by 30 publications

References 41 publications

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

A Comparative Study of Polycrystal/Single‐Crystal LiNi_0.8Co_0.1Mn_0.1O₂ in All‐Solid‐State Li‐Ion Batteries with Halide‐Based Electrolyte under Low Stacking Pressure

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Structural (in)stability and spontaneous cracking of Li-La-zirconate cubic garnet upon exposure to ambient atmosphere

Cited by 30 publications

References 41 publications

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

A Comparative Study of Polycrystal/Single‐Crystal LiNi0.8Co0.1Mn0.1O2 in All‐Solid‐State Li‐Ion Batteries with Halide‐Based Electrolyte under Low Stacking Pressure

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A Comparative Study of Polycrystal/Single‐Crystal LiNi_0.8Co_0.1Mn_0.1O₂ in All‐Solid‐State Li‐Ion Batteries with Halide‐Based Electrolyte under Low Stacking Pressure