Order–Disorder and Mobility of Li+ in the β′- and β-LiZr2(PO4)3 Ionic Conductors: A Neutron Diffraction Study

Catti, M.; Morgante, N.; Ibberson, R. M.

doi:10.1006/jssc.2000.8658

Cited by 47 publications

(62 citation statements)

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“…1B), a pure LiZr 2 (PO 4 ) 3 phase with rhombohedral structure could only be obtained with zirconium acetate; a triclinic phase with space group C-1 was obtained with other zirconium materials. LiZr 2 (PO 4 ) 3 prepared by solid-state reaction with ZrO 2 as the starting material was reported to change from triclinic to rhombohedral structure at 60°C (13,14). The rhombohedral LiZr 2 (PO 4 ) 3 phase with high Li-ion conductivity was stable at room temperature with zirconium acetate as the starting zirconium salt.…”

mentioning

confidence: 99%

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Zhou

Chen

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

248

221

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A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time.Here, we introduce a solid electrolyte LiZr 2 (PO4) 3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σ Li = 2 × 10 −4 S·cm −1 at 25°C, a high electrochemical stability up to 5. electrolyte has enabled the wireless revolution, but it is not able to power safely an electric road vehicle at a cost that is competitive with the gasoline-powered internal combustion engine (1-4). Safety concerns as well as cost, volumetric energy density, and cycle life have prevented realization of a commercially viable electric road vehicle. To address this problem, considerable effort is being given to the development of a solid Li + or Na + electrolyte that is wet by a metallic lithium or sodium anode and has an alkali ion conductivity σ i > 10 −4 S·cm −1 at the cell operating temperature T op , where a T op ≤ 25°C is desired (5-10). Such a development would allow new as well as traditional strategies for the cathode. Wetting of the solid electrolyte surface is desired not only because it prevents dendrite formation and growth during plating of an alkali metal anode, but also because wetting constrains the anode volume change in a charge/ discharge cycle to be perpendicular to the anode/electrolyte interface, thereby allowing a long cycle life. Therefore, the shear modulus of the electrolyte may not be critical where lithium wets the electrolyte surface.Ceramic oxide electrolytes offer a large energy gap between their conduction and valence bands, which can allow realization of a battery cell with a large energy separation between the anode and cathode chemical potentials without either reduction or oxidation of the electrolyte by an electrode (2). However, if an alkali-metal anode reduces the solid electrolyte, formation of a stable solid-electrolyte interphase (SEI) that conducts the working Li + or Na + ion is acceptable if the Li + or Na + transfer across the SEI has a low resistance. Although many ceramic solid Li + electrolytes have been investigated, they are easily reduced by Li metal and/or they have failed to block dendrite formation and growth into their grain boundaries (SI Appendix, Fig. S1). However, the rhombohedral structure of the Na electrolyte Na 1+3x Zr 2 (Si x P 1-x O 4 ) 3 (11), NASICON, which was developed over 45 y ago, has recently been used in a cell design in which a seawater cathode provides the sodium of the anode (12).The stability of the solid electrolyte on contact with a lithium anode is a critical issue. If a lithium anode reduces the electrolyte, (i) the electrolyte may become an electronic conductor, (ii) an interface layer may form that blocks Li + transfer, or (iii) a...

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confidence: 99%

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Zhou

Chen

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

248

221

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“…Both of these sites have a minority occupation and so this unacceptably short Li þ Á Á Á Li þ separation can be avoided by local ordering of lithium such that only no two adjacent sites are simultaneously occupied. [94] Both of these two sites, Li(1) and Li(2), are found within a single large cavity within the structure that is bounded by nine oxide anions within 3.1 Å of either of the two lithium sites. This extra-framework space is clearly too large to provide a bonding environment for a lithium cation located in the centre of the void and so both Li(1) and Li(2) sites are displaced from the centre and achieve distorted tetrahedrally coordinated environments.…”

Section: Lithium Conduction In Nasicon-related Phasesmentioning

confidence: 99%

“…The b 0 phase has lower symmetry than its higher temperature parent phase; the transition b to b 0 involves a change in space group symmetry from orthorhombic Pbna to monoclinic P2 1 /n. [94] These two groups are closely related and the difference between the two phases is crucially dependent on the removal of a twofold symmetry axis from Pbna to give P2 1 /n. The absence of this symmetry operation in the lower The lithium cations, shown as light grey spheres, occupy four-coordinate sites within a large cavity in the structure [94] temperature crystal structure requires a doubling of the number of atoms used to describe the structure, i.e.…”

Section: Lithium Conduction In Nasicon-related Phasesmentioning

confidence: 99%

Lithium Ion Conduction in Oxides

Cussen

2010

Functional Oxides

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“…For sodium-free single crystals, very high conductivities (2.7 Â 10 À3 and 0.18 S cm À1 at 25 and 300 C, respectively) and E a ¼ 23 kJ mol À1 were reported [203], but no data are available for ceramics. Two topologically different framework types with the general formula Li x M 2 T 3 O 12 [1, 2, 6, 10-13, [204][205][206][207][208][209][210][211][212] are based on lanterns of two MO 6 octahedra corner-linked with three TO 4 tetrahedra (Figure 7.21, I). One of these frameworks (R), typified by LiTi 2 (PO 4 ) 3 , is of the NASICON type (see Figure 7.15), with the lanterns in parallel orientation; in another framework (P), typified by Li 3 M 2 (PO 4 ) (M ¼ Sc, Cr, Fe), the lanterns are inclined alternatively in opposite directions (Figure 7.21, II).…”

Section: Mixed Framework Of Oxygen Octahedra and Tetrahedramentioning

confidence: 99%

Alkali Metal Cation and Proton Conductors: Relationships between Composition, Crystal Structure, and Properties

Avdeev¹,

Nalbandyan²,

Shukaev³

2009

Solid State Electrochemistry I

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The aim of this chapter is to provide an overview of materials where fast transport of alkali metal cations and protons is observed. A general discussion of factors affecting conductivity and techniques used to study ion migration paths is followed by a review of the large number of cation conductors. Materials with large alkali ions (Na-Cs) are often isostructural and therefore examined as a group. The lithium conductors with unique crystal structure types and proton conductors with unique conduction mechanisms are also discussed.

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Order–Disorder and Mobility of Li+ in the β′- and β-LiZr2(PO4)3 Ionic Conductors: A Neutron Diffraction Study

Cited by 47 publications

References 17 publications

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Lithium Ion Conduction in Oxides

Alkali Metal Cation and Proton Conductors: Relationships between Composition, Crystal Structure, and Properties

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