Effect of Y substitution for Nb in Li5La3Nb2O12 on Li ion conductivity of garnet-type solid electrolytes

Narayanan, Sumaletha; Thangadurai, Venkataraman

doi:10.1016/j.jpowsour.2011.05.031

Cited by 48 publications

(50 citation statements)

References 29 publications

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“…The peak close to 0 ppm indicates the octahedral coordination of Al, while the other peak close to 70 ppm indicates the tetrahedral coordination of Al. 8,16,[22][23][24] Geiger et al proposed that the octahedral sites occupied by Al 3+ could lead to distortion. 25 It is possible that Al 3+ substitutes for Li + sites and creates lithium vacancies in the structure which affect the structural stabilization.…”

Section: Resultsmentioning

confidence: 99%

“…[5][6][7][8] It is known that volatilization of lithium occurs in the furnace, therefore, several researchers commonly compensate with a 10 wt.% excess lithium precursors.…”

mentioning

confidence: 99%

“…1,2 However, the synthesis of high bulk Li ion conducting garnet-type metal oxidebased lithium ion conductors is a challenging process, very sensitive to preparation conditions used, that are not yet fully characterized. For example, Li 7 La 3 Zr 2 O 12 calcined at 1230…”

mentioning

confidence: 99%

“…3,4 Traditional solid-state techniques are the most commonly used to synthesize garnet-type metal oxides, but usually require the highest sintering temperature resulting in the production of large particles. [5][6][7][8] It is known that volatilization of lithium occurs in the furnace, therefore, several researchers commonly compensate with a 10 wt.% excess lithium precursors. 3,9,10 Al-doped Li 7 La 3 Zr 2 O 12 prepared without adding any excess lithium salts during synthesis, but varying the processing using powder cover condition for sintering, greatly affects the morphology, grain size and density.…”

mentioning

confidence: 99%

“…[5][6][7][8] It is known that volatilization of lithium occurs in the furnace, therefore, several researchers commonly compensate with a 10 wt.% excess lithium precursors. 3,9,10 Al-doped Li 7 La 3 Zr 2 O 12 prepared without adding any excess lithium salts during synthesis, but varying the processing using powder cover condition for sintering, greatly affects the morphology, grain size and density. 11 Attempts have also been made to reduce the sintering temperature and improve the control of stoichiometry via wet chemical synthesis as well as through additives acting as sintering aids.…”

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confidence: 99%

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Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂

Narayanan

Hitz

Wachsman

et al. 2015

J. Electrochem. Soc.

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Volatility of lithium during preparation of lithium-stuffed garnet-type metal oxide solid Li ion electrolytes is a common problem, which affects phase formation, ionic conductivity, mechanical strength and density. Synthesis of Li-stuffed garnets has been performed generally using the conventional solid-state reactions at elevated temperature in air. The present study describes the effect of excess LiNO 3 (2.5 to 15 wt.%) addition during the ceramic synthesis on the structural and electrical properties of garnet-type Li 6 La 3 Ta 1.5 Y 0.5 O 12 . Powder X-ray diffraction (PXRD) confirmed that cubic phase was formed in all tested cases, and there is no significant variation in lattice parameter with amount of excess LiNO 3 used. However, increasing amounts of excess lithium decreased inter-particle contact and increased grain growth during sintering, producing sharply varied microstructures. PXRD showed no secondary phase and scanning electron microscopy (SEM) analysis showed rather uniform morphology and absence of "glassy" materials at the grain-boundaries. The bulk Li ion conductivity was found to increase with amount of excess lithium, reaching a maximum room temperature conductivity of 1.62 × 10 −4 Scm −1 for the sample prepared using 10 wt.% excess LiNO 3 . Raman microscopy study indicated the presence of Li 2 CO 3 in all aged Li 6 La 3 Ta Li-stuffed garnet-type metal oxides have been considered as a potential candidate solid electrolyte material to replace conventional organic liquid based Li ion conducting electrolytes in Li-ion batteries, since members of garnet solid electrolytes exhibit high bulk ion conductivity of 10 −4 -10 −3 Scm −1 at room temperature. Furthermore, some of the garnet-type electrolytes show excellent chemical stability against reaction with elemental Li, Li-ion insertion or intercalation cathodes and high electrochemical stability window.1,2 However, the synthesis of high bulk Li ion conducting garnet-type metal oxidebased lithium ion conductors is a challenging process, very sensitive to preparation conditions used, that are not yet fully characterized. For example, Li 7 La 3 Zr 2 O 12 calcined at 1230• C results in highly conducting (7 × 10 −4 Scm −1 at room temperature) cubic phase with a space group Ia-3d whereas a calcining temperature of 980• C leads to tetragonal phase with a space group I4 1 /acd, which showed 2 orders of magnitude less conductive than cubic phase.3,4 Traditional solid-state techniques are the most commonly used to synthesize garnet-type metal oxides, but usually require the highest sintering temperature resulting in the production of large particles. [5][6][7][8] It is known that volatilization of lithium occurs in the furnace, therefore, several researchers commonly compensate with a 10 wt.% excess lithium precursors.3,9,10 Al-doped Li 7 La 3 Zr 2 O 12 prepared without adding any excess lithium salts during synthesis, but varying the processing using powder cover condition for sintering, greatly affects the morphology, grain size and density. 11Attempts h...

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Section: Resultsmentioning

confidence: 99%

“…[5][6][7][8] It is known that volatilization of lithium occurs in the furnace, therefore, several researchers commonly compensate with a 10 wt.% excess lithium precursors.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂

Narayanan

Hitz

Wachsman

et al. 2015

J. Electrochem. Soc.

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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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Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

Gao

et al. 2021

Advanced Energy Materials

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From the discovery of the first fast ionic conductor silver iodide in the early 20th century to the recent discovery of lithium fast ionic conductors with ionic conductivities surpassing those of liquid electrolytes, high ionic conductivity σ has often been associated with low activation energy Ea following the Arrhenius equation. However, the Meyer–Neldel rule (MNR) indicates that the Ea and prefactor σ0 are correlated, suggesting the relation between the Ea and σ is, in fact, complex. In this perspective, the use of the Meyer–Neldel–conductivity plot and a critical descriptor, Meyer–Neldel energy Δ0, to guide the search for fast ionic conductors is proposed. Reported lithium, sodium, and magnesium ionic conductors are categorized into three types, depending on the relative magnitude between the Δ0 and thermal energy (kBT) at the application temperature. The process by which σ can be optimized by tuning Ea for these types of ionic conductors is elaborated. This principle can be widely applied to all ionic conductors that obey the MNR at any application temperature. Furthermore, a pressure‐tuning approach to measure the Δ0 rapidly is developed. These findings establish a previously missing step for designing new ionic conductors with improved ionic conductivity.

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Effect of Y substitution for Nb in Li5La3Nb2O12 on Li ion conductivity of garnet-type solid electrolytes

Cited by 48 publications

References 29 publications

Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂

Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂

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

Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

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Effect of Y substitution for Nb in Li5La3Nb2O12 on Li ion conductivity of garnet-type solid electrolytes

Cited by 48 publications

References 29 publications

Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li6La3Ta1.5Y0.5O12

Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li6La3Ta1.5Y0.5O12

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

Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

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Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂

Effect of Excess Li on the Structural and Electrical Properties of Garnet-Type Li₆La₃Ta_1.5Y_0.5O₁₂