The activation entropy for ionic conduction and critical current density for Li charge transfer in novel garnet-type Li6.5La2.9A0.1Zr1.4Ta0.6O12 (A = Ca, Sr, Ba) solid electrolytes

Kammampata, Sanoop Palakkathodi; Yamada, Hirotoshi; Ito, Tomoko; Paul, R.; Thangadurai, Venkataraman

doi:10.1039/c9ta12193e

Cited by 35 publications

(23 citation statements)

References 62 publications

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“…Impedance characterization during cycling can uncover "softs shorts" and lithium infiltration into the ISE when the bulk resistance of the cell decreases and was already performed as a diagnostic tool. 274,357 If a filament grows completely through the ISE, dissolution of the filament will usually not take place. However, strong Joule heating due to the very high electronic current densities inside the lithium filament 346 can lead to an electronic contact break-off and cell reactivation.…”

Section: Lithium Growth Through Inorganic Solid Electrolytesmentioning

confidence: 99%

Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries

et al. 2020

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Developing reversible lithium metal anodes with high rate capability is one of the central aims of current battery research. Lithium metal anodes are not only required for the development of innovative cell concepts such as lithium–air or lithium–sulfur batteries, they can also increase the energy density of batteries with intercalation-type cathodes. The use of solid electrolyte separators is especially promising to develop well-performing lithium metal anodes, because they can act as a mechanical barrier to avoid unwanted dendritic growth of lithium through the cell. However, inhomogeneous electrodeposition and contact loss often hinder the application of a lithium metal anode in solid-state batteries. In this review, we assess the physicochemical concepts that describe the fundamental mechanisms governing lithium metal anode performance in combination with inorganic solid electrolytes. In particular, our discussion of kinetic rate limitations and morphological stability intends to stimulate further progress in the field of lithium metal anodes.

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Section: Lithium Growth Through Inorganic Solid Electrolytesmentioning

confidence: 99%

Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries

et al. 2020

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“…Such analysis can be applied to different structural families of Li‐ion conductors including LISICONs, [ 74 ] the garnets, [ 143 ] the NASICONs, [ 144 ] and the argyrodites [ 68 ] as well as other thiophosphates such as Li 10 Ge 1– x Sn x P 2 S 12 . [ 135 ] Δ o in all these materials has been found to be ≈15–100 meV as can be seen in Figure 6b, corresponding well to the energy scale of phonons in solids, supporting the tenant of the MEE theory that the migration entropy Δ S m is associated with distribution of absorbed phonons into a multiplicity of microstates.…”

Section: The Physical Origin To Meyer–neldel Rulementioning

confidence: 99%

Phonon–Ion Interactions: Designing Ion Mobility Based on Lattice Dynamics

Muy

Schlem

Shao‐Horn

et al. 2020

Advanced Energy Materials

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been found in numerous materials covering virtually all chemical compositions and crystal structures. [1][2][3] These materials are also critical in many applications, enabling a number of emerging technologies ranging from memristors to smart windows and fuel cells to name a few. [4][5][6][7][8] In particular, solid-state lithium (Li) electrolytes are believed to help with enabling lithium metal anodes, which will increase the energy density of a battery system and usher a new era of electromobility. [9][10][11] Research in solid-state electrolytes has been largely driven by the designs and discoveries of new materials with higher ionic conductivity. [10,12,13] The progress is particular evident in the research of Li-ion [14][15][16] and Na-ion conductors [17] where recent breakthroughs have led to marked increases in room-temperature ionic conductivity rivalling that of liquid electrolytes. [18] These advancements catalyzed research for new ion conductors that can be further record setting in ion conductivity, while also meeting other device-level requirements such as (electro)chemical stability and good mechanical properties, [19][20][21][22][23] both of which prevent contact loss or other morphological instabilities during cycling. [24][25][26][27][28][29][30][31] New descriptors have been proposed to accomplish rational design of new ion conductors and have been used in several high-throughput computational screenings, [13,[32][33][34] which has led to discovery of new promising Li-ion conductors [13] including those in the chloride family [13,[35][36][37] that display not only high ionic conductivity but also good electrochemical stability. [32,33,38,39] The design of new descriptors has also greatly benefited from the renewed interest in the fundamental of ionic conductivity in solids. [40] Here, concepts such as lattice dynamics or bond frustrations have been revisited in particular in light of new advances in computational capabilities to seek fundamental atomistic mechanisms that promote room-temperature superionic conductivity. [41][42][43][44][45] Clearly, in certain materials such as RbAg 4 I 5 , an impressive Ag + conductivity ≈0.25 S cm -1 can be reached, [46] and the questions is how to the reach the same level of ionic conductivity in other polycrystalline ionic conductors such as solid Li + and Na + electrolytes whose conductivity has so far plateaued at ≈24 mS cm -1 [10] and 41 mS cm -1 , [17] respectively.In this progress report, we will highlight one of the approaches to understand fundamental processes responsible for ion conductivity in solid ionic conductors namely the This review is focused on the influence of lattice dynamics on the ionic mobility in superionic conductors in particular solid-state Li-ion conductors. After a succinct review of the static view of ionic conduction, the role of polarizability as the underlying cause of lattice softness is discussed in connection with the anharmonicity and the roles of lattice dynamics on ionic conductivity as proposed in early theories in th...

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“…The cubic phase is unstable at room temperature due to the Coulomb repulsion of Li ions . To stabilize the cubic phase and improve the Li-ion conductivity, various elements such as Al, Ga, Nb, Ca, and Ta have been doped to create Li-ion vacancies and enhance the Li-ion transport pathways. Ta-doped Li 7 La 3 Zr 2 O 12 (LLTZO) shows chemical stability, high relative density, and Li-ion conductivity and has attracted abundant research interest in recent years. − The doping of Ta contributes to lowering the sintering temperature of the cubic phase, leading to a free-flowing liquid phase and a reduction of lithium volatilization. , …”

Section: Introductionmentioning

confidence: 99%

Oriented Attachment Strategy Toward Enhancing Ionic Conductivity in Garnet-Type Electrolytes for Solid-State Lithium Batteries

Qin

Xie

Meng

et al. 2021

ACS Appl. Mater. Interfaces

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Solid-state lithium batteries (SSLBs) based on garnet-type solid-state electrolytes (SSEs) have attracted much attention due to their high energy density and chemical stability. However, poor room-temperature ionic conductivity and low density of SSEs induced by conventional preparation routes limit their potential future applications. In this work, an oriented attachment strategy is employed to enhance the Li-ion conductivity and density of garnet-type SSE Li6.5La3Zr1.5Ta0.5O12 by introducing La2O3 nanoparticles. The oriented attachment of the ZrO2(Ta2O5) matrix mediates the epitaxial growth of the La–Zr(Ta)–O intermediate phase due to the addition of La2O3 nanoparticles. Continuous Li-ion transport pathways along grain boundaries are produced by the combination of residual La2O3 and gas Li2O. A densification interface is obtained when 10 wt % La2O3 is doped. The maximum value of Li-ion conductivity reaches 8.20 × 10–4 S·cm–1, with a relative density of 97.3%. SSLBs with a LiFePO4 cathode showing a stable cycling performance with a discharge capacity of 123.1 mA·h·g–1 and a Coulombic efficiency of 99.2% after 300 cycles (0.5C) at room temperature. This work is comparable to the state-of-the-art methodology, which provides a feasible approach to creating SSEs with high performances for SSLBs.

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The activation entropy for ionic conduction and critical current density for Li charge transfer in novel garnet-type Li_6.5La_2.9A_0.1Zr_1.4Ta_0.6O₁₂ (A = Ca, Sr, Ba) solid electrolytes

Abstract: Schematic representation of Li growth during DC polarization experiments in the investigated garnet-type metal oxides.

Cited by 35 publications

References 62 publications

Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries

Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries

Phonon–Ion Interactions: Designing Ion Mobility Based on Lattice Dynamics

Oriented Attachment Strategy Toward Enhancing Ionic Conductivity in Garnet-Type Electrolytes for Solid-State Lithium Batteries

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