Lithium and hydrogen ions transport in materials with NASICON structure

Стенина, И. А.; Pinus, I. Yu.; Ребров, А. В.; Yaroslavtsev, A. B.

doi:10.1016/j.ssi.2003.12.037

Cited by 35 publications

(10 citation statements)

References 9 publications

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“…Thus, we are led to conclude that the lithium ions in LiHf 2 (PO 4 ) 3 are significantly delocalized between the M1 and M2 centers even at room temperature, which indicates that they have high mobility. This accounts for the fact that the conductivity of LiHf 2 (PO 4 ) 3 is (an order of magnitude) higher than those of LiTi 2 (PO 4 ) 3 and LiZr 2 (PO 4 ) 3 [9,20]. Above the phase transition of LiZr 2 (PO 4 ) 3 to its hexagonal polymorph, accompa nied by thermal activation of defects, the high tem perature conductivity of LiZr 2 (PO 4 ) 3 is nearly identi cal to that of LiHf 2 (PO 4 ) 3 [20].…”

Section: Resultsmentioning

confidence: 96%

“…This accounts for the fact that the conductivity of LiHf 2 (PO 4 ) 3 is (an order of magnitude) higher than those of LiTi 2 (PO 4 ) 3 and LiZr 2 (PO 4 ) 3 [9,20]. Above the phase transition of LiZr 2 (PO 4 ) 3 to its hexagonal polymorph, accompa nied by thermal activation of defects, the high tem perature conductivity of LiZr 2 (PO 4 ) 3 is nearly identi cal to that of LiHf 2 (PO 4 ) 3 [20]. The conductivity of hexagonal LiTi 2 (PO 4 ) 3 is lower than that of LiHf 2 (PO 4 ) 3 throughout the temperature range stud ied (300-870 K) [9].…”

Section: Resultsmentioning

confidence: 96%

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Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

et al. 2013

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Li 1 + x Hf 2 -x Sc x (PO 4 ) 3 (x = 0-0.3) NASICON type mixed phosphates have been synthesized and characterized by X ray diffraction, nuclear magnetic resonance, and impedance spectroscopy. The results demonstrate that the materials with 0 ≤ x ≤ 0.1 have a hexagonal structure, whereas in the range 0.1 < x ≤ 0.2 the materials consist of a mixture of hexagonal and orthorhombic phases. The x = 0.3 material has an orthor hombic NASICON structure. Doping with scandium leads to an increase in ionic conductivity in the range 0 < x ≤ 0.1.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 96%

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

et al. 2013

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“…c) The final stoichiometry of the material is very important, especially for the end members, since small deviations of charge carriers (or vacancies at the other extreme) of only 1-2 % can lead to conductivity changes by several orders of magnitude. [49,50] Yttrium substitutions:…”

Section: Resultsmentioning

confidence: 99%

Survey of Zirconium‐Containing NaSICON‐type Solid‐State Li⁺ Ion Conductors with the Aim of Increasing Reduction Stability by Partial Cation Substitution

Loutati

Odenwald

Aktekin

et al. 2022

Batteries & Supercaps

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Various compositions of the series Li 1 + x M 3 +x Zr 2À x (PO 4 ) 3 where M 3 + = Al 3 + , Sc 3 + , Y 3 + were prepared by solution-assisted solidstate reaction, since they could have a higher reduction stability as solid electrolytes in lithium batteries than in germanium-or titanium-containing materials. The influence of substitution on crystallographic parameters, density, and ionic conductivity were investigated. The cation substitution of M 3 + (M = Al, Sc, Y) for Zr 4 + in LiZr 2 (PO 4 ) 3 stabilizes the rhombohedral NaSICON structure (space group R � 3c) at room temperature and increases the ionic conductivity significantly. Here, at 25 °C and with a consistent relative density of 94 %-96 %, an ionic conductivity of 2.7 × 10 À 5 S cm À 1 , 6.7 × 10 À 5 S cm À 1 , and 3.6 × 10 À 6 S cm À 1 was achieved with the compositions Li 1.2 Sc 0.2 Zr 1.8 (PO 4 ) 3 , Li 1.2 Y 0.2 Zr 1.8 (PO 4 ) 3 , and Li 1.2 Al 0.2 Zr 1.8 (PO 4 ) 3 , respectively . In comparison with Li 1 + x Sc x Zr 2À x (PO 4 ) 3 , the Y 3 + substitution in LiZr 2 (PO 4 ) 3 enhanced the ionic conductivity slightly and denoted the maximum Li + ionic conductivity obtained at room temperature. However, substitution with Al 3 + decreased the ionic conductivity. For the first time, this work provides a complete overview of three series of solid Li-ion conductors in the Li 2 O-M 2 O 3 -ZrO 2 -P 2 O 5 system where M = Al, Sc, Y. Noticeable differences in the chemistry of resulting compounds were observed, which likely depend on the ionic radius of the cations being substituted. The series with Sc showed complete miscibility from x = 0 to x = 2 with a continuous change of the NaSICON polymorphs. The series with Y showed a solubility limit at about x = 0.3 and higher substitution levels led to the increasing formation of YPO 4 . The series with Al exhibited continuously decreasing ionic conductivity until x = 1, whereupon the investigation was terminated due to its very low conductivity of about 10 À 10 S cm À 1 .

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“…NASICON, can also play a signicant role in determining the conduction mechanisms. 156 The nature of the interface surely changes when a new class of inorganic ller components is employed. Recently re-developed halide-based ion conductors are revealed to possess better electrochemical stability than suldes, with comparably high ionic conductivity.…”

Section: Conductive Inorganic Component: Importance Of the 3d Networkmentioning

confidence: 99%

Polymer-based hybrid battery electrolytes: theoretical insights, recent advances and challenges

et al. 2021

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Lithium and hydrogen ions transport in materials with NASICON structure

Cited by 35 publications

References 9 publications

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

Survey of Zirconium‐Containing NaSICON‐type Solid‐State Li⁺ Ion Conductors with the Aim of Increasing Reduction Stability by Partial Cation Substitution

Polymer-based hybrid battery electrolytes: theoretical insights, recent advances and challenges

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Lithium and hydrogen ions transport in materials with NASICON structure

Cited by 35 publications

References 9 publications

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

Survey of Zirconium‐Containing NaSICON‐type Solid‐State Li+ Ion Conductors with the Aim of Increasing Reduction Stability by Partial Cation Substitution

Polymer-based hybrid battery electrolytes: theoretical insights, recent advances and challenges

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Survey of Zirconium‐Containing NaSICON‐type Solid‐State Li⁺ Ion Conductors with the Aim of Increasing Reduction Stability by Partial Cation Substitution