On the influence of the cation vacancy on lithium conductivity of Li1+xRxTi2−x(PO4)3 Nasicon type materials

Arbi, K.; Jiménez, Ricardo; Салкус, Т.; Орлюкас, А.Ф.; Sanz, J.

doi:10.1016/j.ssi.2014.10.016

Cited by 21 publications

(19 citation statements)

References 27 publications

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“…(All the relevant data are obtained from refs. [ 1,6,17,23,24,33,36,37,39–64 ] and detailed information can be found in Tables S1–S7, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

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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“…(All the relevant data are obtained from refs. [ 1,6,17,23,24,33,36,37,39–64 ] and detailed information can be found in Tables S1–S7, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

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

Gao

et al. 2021

Advanced Energy Materials

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“…134 (c) MEM-reconstructed negative nuclear density maps. 52 [122][123][124][125][126][127][128][129][130][131] In particular, a high lithium conductivity at room temperature, 7 Â 10 À4 S cm À1 was reported in the case of Li 1.3 R 0.3 Ti l.7 (PO 4 ) 3 (R = Al 3+ ), abbreviated as LATP. 123 Similar effects caused by trivalent cation doping at M sites are also observed in the LiGe 2 (PO 4 ) 3 phase and an ion conductivity of 2.4 Â 10 À4 S cm À1 can be achieved in well-known Li 1+x Al x Ge 2Àx (PO 4 ) 3 , abbreviated as LAGP.…”

Section: Energy and Environmental Sciencementioning

confidence: 99%

New horizons for inorganic solid state ion conductors

Zhang

Shao

Lotsch

et al. 2018

Energy Environ. Sci.

1,043

955

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“…The partial substitution of Ti 4+ by trivalent cations such as Al 3+ , Sc 3+ , Ga 3+ , Fe 3+ , In 3+ , and Cr 3+ in Li 1+ x R x Ti 2– x (PO 4 ) 3 materials, is compensated by lithium, improving ion conductivity. − In these compounds, correlations between structure, preparation conditions, and densification of pellets have been previously reported. In particular, Aono et al reported high lithium conductivity at room temperature, 7 × 10 –4 S·cm –1 , in Li 1.3 R 0.3 Ti 1.7 (PO 4 ) 3 compounds (R 3+ = Al 3+ or Sc 3+ ).…”

Section: Introductionmentioning

confidence: 97%

Cation Miscibility and Lithium Mobility in NASICON Li_1+xTi_2–xSc_x(PO₄)₃ (0 ≤ x ≤ 0.5) Series: A Combined NMR and Impedance Study

et al. 2017

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Rhombohedral NASICON compounds with general formula LiTiSc(PO) (0 ≤ x ≤ 0.5) have been prepared using a conventional solid-state reaction and characterized by X-ray diffraction (XRD), nuclear magnetic resonance (NMR), and impedance spectroscopy. The partial substitution of Ti by Sc and Li in pristine LiTi(PO) increases unit-cell dimensions and the number of charge carriers. In Sc-rich samples, the analysis of XRD data and Li/Li, P, andSc MAS NMR spectra confirms the presence of secondary LiScO and LiScPO phases that reduce the amount of lithium incorporated in the NASICON phase. In samples with x < 0.3, electrostatic repulsions between Li ions located at M1 and M3 sites increase Li mobility. For x ≥ 0.3, ionic conductivity decreases because of secondary nonconducting phases formed at grain boundaries of the NASICON particles (core-shell structures). For x = 0.2, high bulk conductivity (2.5 × 10 S·cm) and low activation energy (E = 0.25 eV) measured at room temperature make LiTiSc(PO) one of the best lithium ionic conductors reported in the literature. In this material, the vacancy arrangement enhances Li conductivity.

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On the influence of the cation vacancy on lithium conductivity of Li1+xRxTi2−x(PO4)3 Nasicon type materials

Cited by 21 publications

References 27 publications

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

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

New horizons for inorganic solid state ion conductors

Cation Miscibility and Lithium Mobility in NASICON Li_1+xTi_2–xSc_x(PO₄)₃ (0 ≤ x ≤ 0.5) Series: A Combined NMR and Impedance Study

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On the influence of the cation vacancy on lithium conductivity of Li1+xRxTi2−x(PO4)3 Nasicon type materials

Cited by 21 publications

References 27 publications

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

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

New horizons for inorganic solid state ion conductors

Cation Miscibility and Lithium Mobility in NASICON Li1+xTi2–xScx(PO4)3 (0 ≤ x ≤ 0.5) Series: A Combined NMR and Impedance Study

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Product

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Cation Miscibility and Lithium Mobility in NASICON Li_1+xTi_2–xSc_x(PO₄)₃ (0 ≤ x ≤ 0.5) Series: A Combined NMR and Impedance Study