Synthesis, ionic conductivity, and chemical compatibility of garnet-like lithium ionic conductor Li5La3Bi2O12

Gao, Yue; Wang, X.P.; Wang, W.G.; Zhuang, Zhi; Zhang, D.M.; Qian, Fang

doi:10.1016/j.ssi.2010.08.012

Cited by 49 publications

(34 citation statements)

References 27 publications

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“…Li et al pointed out that the cubic garnet phase is difficult to obtain for x>7.0 and that x=7.5 is the upper limit of x in a A 3 B 2 Li x O 12 garnet framework due to the short Li + -Li + distances, which destabilize the crystal structure. Their studies on Li 7-x La 3 Zr 2-x Ta x O 12 and LLZ showed an optimized ratio of Li occupancy and vacancy of the octahedral sites for highly Li-ion conductive A 3 B 2 Li x O 12 is around 3:1 which gives the Li content of 6.4 ≤ x ≤ 6.6 [20,29,30]. Figure 4(b) also shows a strong dependency of the conductivity on the Li concentration from our mixed phase LLZ:Al which have major phase in tetragonal.…”

Section: Resultsmentioning

confidence: 99%

“…In the oxide class of materials, materials with garnet structure have been recently attracted a lot of attention due to their high total Li-ion conductivity. Among these materials, Li 7 La 3 Zr 2 O 12 (LLZ) is one of the highest reported Li-ion conductors with conductivity of 4×10 −4 S cm −1 at room temperature [10][11][12][13][14][15]. This type of materials with their inherent safety (nonflammable), easy handling (during processing etc.…”

Section: Introductionmentioning

confidence: 99%

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High conductivity of mixed phase Al-substituted Li7La3Zr2O12

et al. 2015

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Al-substituted Li 7 La 3 Zr 2 O 12 (LLZ:Al) was synthesized via conventional solid state reaction. Different dwell times at sintering temperature of 1200°C led to a varying Li content in LLZ:Al which significantly affected the Li-ion conductivity. Electrochemical impedance spectroscopy and X-ray diffraction were used to characterize the sintered pellets which showed a maximum total ionic conductivity of~3 × 10 −4 S cm −1 at room temperature although the samples were composed of cubic and tetragonal LLZ:Al, with the tetragonal phase as its major phase. Inductively coupled plasma optical emission spectroscopy revealed that the Li content steadily decreased from 7.5 to 6.5 Li per formula unit with increasing sintering time. The highest conductivity was observed from the sample with the lowest Li concentration at 6.5 per formula unit. Scanning electron microscopy images revealed the formation of large grains, about 500 μm in diameter, which additionally could be the reason for achieving high total Li-ion conductivity. Electrochemical tests showed that mixed phase LLZ:Al is stable against metallic Li up to 8 V.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

et al. 2015

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“…Figure 1 shows the powder X-ray diffraction (PXRD) patterns for the synthesized solid after water evaporation and calcination at different temperatures for 3 h. Heating up the sample at a higher temperature, intensifies the crystallinity. The major peaks indicated formation of tetragonal structure of garnet-type Li 7 La 3 Zr 2 O 12 . Simulated PXRD patterns of tetragonal and cubic garnet-type Li 7 La 3 Zr 2 O 12 structure are shown for comparison in Figure 1.…”

Section: Methodsmentioning

confidence: 99%

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

Zarabian

Bartolini

Pereira‐Almao

et al. 2017

J. Electrochem. Soc.

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Li ion half-cell electrode-based configuration was prepared by spin-coating using precursor of Li-stuffed garnet with intended composition of Li 7 La 3 Zr 2 O 12 on LiCoO 2 . The main goal of this study was lowering the heat-treatment to 400 • C, which is well below the chemical reaction temperature of these phases. Liquid precursor of the nominal compound was prepared and spin-coated on the top surface of MgO(100) and LiCoO 2 pellets until the appropriate thickness was obtained. Electrochemical impedance spectroscopy (EIS) was used to understand the resistance and capacitance behavior of the electrolyte and electrolyte-electrode interface. The ac impedance of half-cell shows semicircles, corresponding to the response from bulk electrolyte, second phase and interface. The interfacial region between LiCoO 2 and Li-La-Zr-O film was deeply studied with X-ray photoelectron spectroscopy (XPS) depth profile analysis. XPS results show that Co diffuses from the substrate toward the solid electrolyte; Li depletes in the interface region, and moves to the top surface, which changes the electronic structure of Co to a multiplicity of reduced forms. The present study shows that even at 400 • C, the Li-stuffed garnet precursor and LiCoO 2 cathode seem to form reaction products, suggesting that is critical for applications to develop protecting layers between the cathodes and Li-stuffed garnet electrolytes. Switching from an organic polymer-based Li ion electrolyte to a ceramic Li ion electrolyte in conventional Li ion batteries is expected to allow for higher energy density, improve safety and prolong lifetime. These, all-solid-state Li batteries can also be miniaturized, which will streamline the packing design and save cargo space. A solid electrolyte has to have several criteria to be able to use in the Li ion batteries such as high ionic conductivity at room temperature, high Li + ion transference number, chemical stability versus the Li cathodes and the Li anodes during preparation and battery operation, sustainability and economic feasibility.1-3 Although all-solid-state batteries offer lots of advantages over conventional liquid and polymer based batteries, the widespread applications of currently developed solid-state (ceramic) Li ion electrolytes have been postponed by low conductivity and or high reactivity with the electrodes which impede reaching high power density required for electric vehicles. 4,5 Li-stuffed garnet is a promising type of solid electrolyte offering an advantage of very high electrochemical stability window (∼6 V versus Li/Li + for Zr and Ta-based garnets), which opens up the possibility of using alternative cathodes and anodes for high voltage applications. It solely allows Li ions to move, and reduces the chance of capacity fading by unwanted reactions and or self-discharging. It is benign and resistant to Li dendrite electroplating.6-8 Interfacial resistance of Li stuffed garnet with Li metal and LiCoO 2 has been the scope of some recent studies targeting developing high performance battery f...

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“…Moreover, the formation of interphase during the high‐temperature solid‐state reactions such as LiAlSiO 4 or LiGaO 2 at the grain boundaries can also contribute to the high conductivities of LLZO . These garnet‐type materials have a high conductivity, wide electrochemical window, and low electronic conductivity; however, they are limited by their reactions with adsorbed H 2 O or CO 2 . Therefore, it is necessary to increase the stability of garnet‐type SSEs against moisture and CO 2 in air.…”

Section: Synthesismentioning

confidence: 99%

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

et al. 2018

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All-solid-state lithium batteries (ASSLBs) have the potential to revolutionize battery systems for electric vehicles due to their benefits in safety, energy density, packaging, and operable temperature range. As the key component in ASSLBs, inorganic lithium-ion-based solid-state electrolytes (SSEs) have attracted great interest, and advances in SSEs are vital to deliver the promise of ASSLBs. Herein, a survey of emerging SSEs is presented, and ion-transport mechanisms are briefly discussed. Techniques for increasing the ionic conductivity of SSEs, including substitution and mechanical strain treatment, are highlighted. Recent advances in various classes of SSEs enabled by different preparation methods are described. Then, the issues of chemical stabilities, electrochemical compatibility, and the interfaces between electrodes and SSEs are focused on. A variety of research addressing these issues is outlined accordingly. Given their importance for next-generation battery systems and transportation style, a perspective on the current challenges and opportunities is provided, and suggestions for future research directions for SSEs and ASSLBs are suggested.

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Synthesis, ionic conductivity, and chemical compatibility of garnet-like lithium ionic conductor Li5La3Bi2O12

Cited by 49 publications

References 27 publications

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

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Synthesis, ionic conductivity, and chemical compatibility of garnet-like lithium ionic conductor Li5La3Bi2O12

Cited by 49 publications

References 27 publications

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO2Cathode Interface for All-Solid-State Li Batteries

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

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X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries