Recent Progress in Garnet-Type Structure Solid Li Ion Electrolytes: Composition – Structure – Ionic Conductivity Relationship and Chemical Stability Focused

Truong, Lina; Narayanan, Sumaletha; Thangadurai, Venkataraman

doi:10.1149/04527.0021ecst

Cited by 10 publications

(6 citation statements)

References 14 publications

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“…e., number of Li cations per unit-cell volume), the Boltzmann constant k B , and the temperature T . The calculated diffusion coefficients increase with increasing unit-cell size and are in good agreement with the diffusion coefficients in this class of materials, obtained through spectroscopical and electrical methods. , …”

Section: Resultssupporting

confidence: 82%

“…The calculated diffusion coefficients increase with increasing unit-cell size and are in good agreement with the diffusion coefficients in this class of materials, obtained through spectroscopical and electrical methods. 16,35 Temperature-dependent ionic conductivities of all compositions of Li 6 MLa 2 Ta 2 O 12 are shown in Figure 7 between 18 and 100 °C. Reproducible electrical impedance data in air could not be obtained at higher temperatures, due to a degree of history and a kink in the data upon cooling after the pellets were heated to temperatures above 100 °C.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…A common approach to optimize the performance is to replace M or M′ with an aliovalent cation in order to increase the amount of lithium content in the garnet structure. This type of substitution allows the material to maintain a charge balance while also producing compositions with higher Li content which is known to increase Li-ion conductivities, as typified by Li 7 La 3 Zr 2 O 12 , − Li 3+ x Nd 3 Te 2– x Sb x O 12 , , and Li 5 La 3 (Ta/Nb) 2 O 12 . − As a further example, substitution of La 3+ with a divalent alkaline earth cation in Li 5 La 3 Ta 2 O 12 has also been shown to increase the Li content using Ca 2+ , Sr 2+ , , and Ba 2+ . ,− Although this increase in Li content ultimately leads to an enhanced Li-ion conductivity, the difference in the alkaline earth metal is also found to have a significant effect on their ionic conductivities.…”

Section: Introductionmentioning

confidence: 99%

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Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂

Zeier

Zhou

López-Bermúdez

et al. 2014

ACS Appl. Mater. Interfaces

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Inspired by the promising ionic conductivities of the lithium conducting garnets, we present a comparative study on the influence of the ionic radius of M(2+) on the 8-coordinate site and the crystal structure on the ionic transport in the solid solution Li6MLa2Ta2O12. Neutron diffraction and synchrotron diffraction in combination with AC impedance measurements are employed to understand the systematic substitution with different-sized alkaline earth cations M(2+). As may be expected, the unit-cell parameters increase linearly with increasing ionic radius from Ca(2+) over Sr(2+) to Ba(2+), accompanied by an increase in the polyhedral volumes of the dodecahedral, and tetrahedral positions and the ionic conductivities. While the TaO6 octahedral volume remain constant, the anisotropic thermal parameters of the coordinating oxygen anions suggest a high degree of rotational freedom with increasing unit-cell size. These structural parameters lead to lower activation energies because of broader Li conduction pathways and a higher flexibility in the crystal lattice, ultimately controlling the ionic conductivities in this class of materials.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂

Zeier

Zhou

López-Bermúdez

et al. 2014

ACS Appl. Mater. Interfaces

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“…A garnet-type oxide, Li 5+x La 3 Zr x Nb 2−x O 12 with x = 0 − 2 (LLZONb), has been investigated as a solid electrolyte for an all solid-state Li-ion battery due to its high Li ion conductivity (σ Li ) [13,14]. Interestingly, σ Li was found to depend on x and reach a maximum at x = 1.75 at ambient temperature (T ), for reasons currently unknown [15,16].…”

Section: Carrier Density [11]mentioning

confidence: 99%

Macroscopic Electrochemical Properties Clarified by Microscopic Measurements; Present and Future

Shen¹

2014

Proceedings of the International Symposium on Science Explored by Ultra Slow Muon (USM2013)

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Although microscopic measurements, such as, Li-NMR and µ + SR, provide fundamental information on Li-diffusion in solids, it is highly preferable to combine such information with the macroscopic properties in order to obtain a new insight to improve electrochemical properties of the whole battery system and/or to develop new electrode and electrolyte materials. In fact, the comparison between a diffusion coefficient of Li (D Li ) with ionic conductivity provided the number density of mobile Li ions, i.e. carrier density in a garnet-type electrolyte material, Li 5+x La 3 Zr x Nb 1−x O 12 . Furthermore, when D Li obtained by µ + SR is compared with D Li estimated by electrochemical measurements, a reactive surface of the cathode used for the electrochemical measurements was firstly derived as a function of the Li content (x) in the cathode material, Li x (Co 1/3 Ni 1/3 Mn 1/3 )O 2 . Finally, I will make an outlook towards future developments by means of a ultra-slow muon microscope.

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mentioning

confidence: 99%

Defect Strategy in Solid‐State Lithium Batteries

Mi,

Chen,

et al. 2023

Small Methods

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Solid‐state lithium batteries (SSLBs) have great development prospects in high‐security new energy fields, but face major challenges such as poor charge transfer kinetics, high interface impedance, and unsatisfactory cycle stability. Defect engineering is an effective method to regulate the composition and structure of electrodes and electrolytes, which plays a crucial role in dominating physical and electrochemical performance. It is necessary to summarize the recent advances regarding defect engineering in SSLBs and analyze the mechanism, thus inspiring future work. This review systematically summarizes the role of defects in providing storage sites/active sites, promoting ion diffusion and charge transport of electrodes, and improving structural stability and ionic conductivity of solid‐state electrolytes. The defects greatly affect the electronic structure, chemical bond strength and charge transport process of the electrodes and solid‐state electrolytes to determine their electrochemical performance and stability. Then, this review presents common defect fabrication methods and the specific role mechanism of defects in electrodes and solid‐state electrolytes. At last, challenges and perspectives of defect strategies in high‐performance SSLBs are proposed to guide future research.

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Recent Progress in Garnet-Type Structure Solid Li Ion Electrolytes: Composition – Structure – Ionic Conductivity Relationship and Chemical Stability Focused

Cited by 10 publications

References 14 publications

Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂

Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂

Macroscopic Electrochemical Properties Clarified by Microscopic Measurements; Present and Future

Defect Strategy in Solid‐State Lithium Batteries

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Recent Progress in Garnet-Type Structure Solid Li Ion Electrolytes: Composition – Structure – Ionic Conductivity Relationship and Chemical Stability Focused

Cited by 10 publications

References 14 publications

Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li6MLa2Ta2O12

Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li6MLa2Ta2O12

Macroscopic Electrochemical Properties Clarified by Microscopic Measurements; Present and Future

Defect Strategy in Solid‐State Lithium Batteries

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Product

Resources

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Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂

Dependence of the Li-Ion Conductivity and Activation Energies on the Crystal Structure and Ionic Radii in Li₆MLa₂Ta₂O₁₂