Synthesis and Electrophysical Properties of Superionic Conductors Li3M2(PO4)3 (M = Fe, Sc, Cr)

Bykov, A. B.; Dem’yanets, L. N.; Doronin, S. N.; Ivanov-Shits, A. K.; Mel'Nikov, O. K.; Sevast'yanov, B. K.; Тимофеева, В. А.; Chirkin, A. P.

doi:10.1007/978-1-4615-3662-8_4

Cited by 6 publications

(15 citation statements)

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“…The activation energy for Li + migration and the conductivity at 298 K for the Li 3 À 2x Cr 2 À x Ta x (PO 4 ) 3 system. rhombohedral [26] and Li 3 M 2 (PO 4 ) 3 , (M = Sc and Fe) for the monoclinic [27,28] 3 . The Li + -O distance was not same for each coordinated oxygen in the monoclinic structure.…”

Section: Lim III M V (Po 4 ) 3 M Iii M V =Crta Alta Crnb Alnb Gmentioning

confidence: 99%

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

Aono¹

2004

Solid State Ionics

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Section: Lim III M V (Po 4 ) 3 M Iii M V =Crta Alta Crnb Alnb Gmentioning

confidence: 99%

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

Aono¹

2004

Solid State Ionics

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“…All of these are reversible transitions and single crystals suitable for crystallographic characterisation can be cycled through the transitions without excessive degradation. [126] This robustness is probably a result of the modest structural adjustments that occur at both transitions and these are largely limited to changes in the arrangement of the lithium cations, with only relatively small adjustments in the positions of the framework atoms. The room temperature structure contains a fully ordered arrangement of lithium across three, fully occupied sites within the large cavity.…”

Section: Doped Analogues Of Lizr 2 (Po 4 )mentioning

confidence: 99%

“…The transformation to the b polymorph appears to be driven by the disordering of the lithium cations as they are displaced from the fully occupied sites in the room temperature structure and instead distributed over three crystallographically distinct partially occupied sites tending to show highly irregular four and five coordination. [126] This disordering increases further on heating and drives the change in symmetry at 245°C. [127] All three phases show appreciable lithium ion conductivity.…”

Section: Doped Analogues Of Lizr 2 (Po 4 )mentioning

confidence: 99%

“…The activation energy also shows significant anisotropy and varies between 0.38 and 0.62 eV. [126] The high ionic conductivity of g-Li 3 Sc 2 (PO 4 ) 3 can be achieved at room temperature by doping this material with smaller tetravalent cations Ti 4þ and Zr 4þ . At room temperature Li 2.8 (Sc 0.9 Ti 0.1 ) 2 (PO 4 ) 3 and Li 2.8 (Sc 0.9 Zr 0.1 ) 2 (PO 4 ) 3 both crystallise with the orthorhombic structure that is stable in the pure scandium phase above 245°C.…”

Section: Doped Analogues Of Lizr 2 (Po 4 )mentioning

confidence: 99%

“…In stabilising the g polymorph to lower temperatures the conductivity of these doped NASICONs is greatly increased compared with either the b-or a-Li 3 Sc 2 (PO 4 ) 3 phases observed shown as empty triangles and squares respectively [127] below 245°C with a conductivity of 3 Â 10 À3 S cm À1 at 150°C for Li 2.8 (Sc 0.9 Zr 0.1 ) 2 (PO 4 ) 3 as shown in Figure 3.18. The compounds Li 3 Cr 2 (PO 4 ) 3 and Li 3 Fe 2 (PO 4 ) 3 both show the same sequence of structural transitions [125,126] as Li 3 Sc 2 (PO 4 ) 3 . These compounds form orthorhombic fast lithium ion conducting phases above 265°C and 312°C respectively and show conductivities ca 10 À2 S cm À1 at these temperatures.…”

Section: Doped Analogues Of Lizr 2 (Po 4 )mentioning

confidence: 99%

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replacement of liquid electrolyte and has the potential to achieve improved safety, higher energy density, and longer cycle life than current commercial lithiumion batteries with liquid electrolytes. [17] Despite significant research efforts, only a few Li SIC materials exhibit an ionic conductivity of >10 −3 S cm −1 at room temperature, and some Li SICs suffer from limited stability, poor interfacial compatibility, or high cost in processing and manufacturing. [6,7,18] A strong need exists for fundamental understanding of these SIC materials in order to design and discover new Li SIC materials.A Li-ion conductor material is comprised of a mobile Li-ion sublattice hosted in a crystal structural framework of immobile polyanion groups. The empty space in between these polyanion groups hosts Li ions as Li sites and forms interconnected channels. Li ions migrate among the sites through these channels, contributing to overall ionic transport. Well-known crystal structural frameworks of SICs include NASICON structure of LiM 2 (PO 4 ) 3 (M = Ge, Ti, Sn, Hf, Zr) compositions, [19] garnet structure of Li x La 3 M 2 O 12 (5 ≤ x ≤ 7, M = Nb, Ta, Sb, Zr, Sn) compositions, [20] and LGPS-type structure of Li 10+x M 1+x P 2−x S 12 (0 ≤ x ≤ 1, M = Si, Ge, Sn) compositions. [21] Recent studies have demonstrated that the crystal structural framework determines Li sites, migration pathways, and the energy landscape, and particular crystal structural frameworks are optimal for low energy barrier Li ion migration. [10,22,23] For example, the crystal structural framework with a body-centered cubic (bcc) anion sublattice, such as found in LGPS and Li 7 P 3 S 11 , has been shown to have an energy landscape with the lowest barrier compared to other anion sublattices, such as in facecentered cubic and hexagonal close packed sublattices. [10] However, some SICs with crystal structural frameworks of non-bcc anion sublattices, such as lithium garnet (e.g., LLZO) and lithium NASICON (e.g., LATP), also exhibit high Li + conductivities as high as ≈10 −3 S cm −1 at RT. It remains an open question as to what features of these crystal structure frameworks enable super-ionic conduction.Due to their unique crystal structural frameworks, SIC materials have highly mobile Li-ion sublattices, which are drastically different from those in typical solids (Figure 1). The disordered Li sublattice of SICs facilitates the transport of a large number of Li ions and yields high ionic conductivity. In the disordered Li sublattice, the Li-ion diffusion mechanism is also distinctive As technologically important materials for solid-state batteries, Li superionic conductors are a class of materials exhibiting exceptionally high ionic conductivity at room temperature. These materials have unique crystal structural frameworks hosting a highly conductive Li sublattice. However, it is not understood why certain crystal structures of the super-ionic conductors lead to high conductivity in the Li sublattice. In this study, using topological analysis and ab initio molecula...

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Synthesis and Electrophysical Properties of Superionic Conductors Li3M2(PO4)3 (M = Fe, Sc, Cr)

Cited by 6 publications

References 5 publications

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

Lithium Ion Conduction in Oxides

Crystal Structural Framework of Lithium Super‐Ionic Conductors

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