A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy

Peréz-Estébanez, Marta; Isasi-Marín, J.; Többens, Daniel M.; Rivera-Calzada, A.; León, Carlos

doi:10.1016/j.ssi.2014.07.018

Cited by 75 publications

(53 citation statements)

References 48 publications

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“…Importantly, the low sintering temperatures prevent, in particular, Li loss during the final annealing step. 36 The replacement of Ti 4+ by Al 3+ ions needs extra Li ions for charge compensation and these ions occupy the interstitial voids. It is composed of alternating, corner-sharing [PO 4 ] tetrahedra and [TiO 6 ] octahedra, in which Li is reported to occupy mainly M1 sites (see Fig.…”

Section: Introductionmentioning

confidence: 99%

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Epp

Hammer

et al. 2015

Phys. Chem. Chem. Phys.

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The realization of large powerful all-solid-state batteries is still hampered by the availability of environmentally friendly and low-cost Li ion conductors that can easily be produced on a large scale and with high reproducibility. Advanced solid electrolytes benefit from fast ion-selective transport and non-flammability, but they may have low electrochemical stability with respect to Li metal. Sol-gel-synthesized lithium titanium aluminum phosphate Li(1.5)Al(0.5)Ti(1.5)(PO4)3 (LATP), which was prepared via a new synthesis route taking advantage of an annealing step at relatively low temperatures, has the potential to become one of the major players in this field although it may suffer from reduction upon direct contact with metallic lithium. Its ion dynamics is, however, as yet poorly understood. In the present study, (7)Li nuclear magnetic resonance (NMR) spectroscopy was used to monitor the key Li jump processes on the atomic scale. NMR relaxation clearly reveals heterogeneous dynamics comprising distinct ultra-fast and slower diffusion processes. The high Li ion self-diffusion coefficients deduced originate from a rapid Li exchange with activation energies as low as 0.16 eV which means that sol-gel synthesized LATP is superior to other solid electrolytes. Our NMR results fully support recent theoretical investigations on the underlying diffusion mechanism, indicating that to rapidly jump from site to site, the ions use interstitial sites connected by low-energy barriers in LATP.

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Section: Introductionmentioning

confidence: 99%

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Epp

Hammer

et al. 2015

Phys. Chem. Chem. Phys.

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“…At sintering temperatures as low as 850°C, the reaction was not completed. All diffraction lines of the samples sintered at 900, 950, and 1,000°C could be indexed as the NASICON-type structure (Perez-Estebanez et al, 2014). Figure 2 shows the relative density of Li1.5Al0.5Ge0.2Ti1.3 (PO4)3 pellets sintered at various temperatures.…”

Section: Methodsmentioning

confidence: 99%

High Lithium-Ion-Conducting NASICON-Type Li1+xAlxGeyTi2−x−y(PO4)3 Solid Electrolyte

et al. 2016

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A water-stable solid electrolyte is a key material without which aqueous lithium-air batteries could not be operated. In this study, we have examined the electrical conductivity and mechanical properties of a water-stable lithium-ion-conducting solid electrolyte, Li1+xAlxGeyTi2−x−y(PO4)3 with the NASICON-type structure, as a function of the Al and Ge content. Li1+xAlxGeyTi2−x−y(PO4)3 was synthesized by the conventional solid-state reaction method. The highest lithium-ion conductivity of 1.0 × 10 −3 S cm −1 at 25°C and the highest three-point bending strength of 90 N mm −2 at room temperature were observed for a pellet of Li1.45Al0.45Ge0.2Ti1.35(PO4)3 sintered at 900°C.

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“…The bulk density of 2.91 g/cm 3 at 800 °C sintering temperature was observed for LTAP sample. Further increase in temperature, suddenly decreases the density to 2.65 g/cm 3 at 850 °C and the density further increase to 2.83 g/cm 3 . Bulk density decreases with increase in temperature from 900 to 950 °C with slight increase of density at 1000 °C sintering temperature.…”

Section: Characterization Techniquesmentioning

confidence: 95%

“…The decrease in bulk density which occurs at 950 and 1000 °C for LTAP-0.2 could be as a result of voids that probably do occur between the individual grains which lead to low density of ceramic materials. High densification of crystal grains occurs at 800 °C sintering temperature with bulk density of 2.91 g/cm 3 . At this temperature, the sample is denser with minimum or no voids along the grain boundaries and resulted in higher densification.…”

Section: Characterization Techniquesmentioning

confidence: 99%

“…Much attention has been paid to rechargeable lithium batteries as a future energy storage due to its higher energy density and longer charge retention [2]. Lithium-based solid electrolyte is one of the best candidates for the application in batteries due to its high potential and low weight for high-energy density storage in batteries [3]. The lithium transition metal phosphates have found application in the field of electrochemical energy storage, especially those with Nasicon structure, because of their good electrochemical performances and capability to answer safety concerns surrounding oxide chemistry [4].…”

Section: Introductionmentioning

confidence: 99%

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Physical characterization and electrical conductivity of Li1.2Ti1.8Al0.2(PO4)3 and Li1.2Ta0.9Al1.1(PO4)3 NASICON material

Mohammed

Mayzan²,

Esa³

et al. 2018

IJIE

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Despite the attractive features of NASICON LATP, it is not clear whether the high conductivity of Li 1+x Ti 2−x Al x (PO 4) 3 composition is intrinsic to the structure or the formation of secondary phases that favors sintering and eliminate grain-boundary resistance is the cause of high conductivity [5], [6]. Towards this end, lithium-ion conduction of mixed-metal NASICON-phases of the formula, LiM v M iii (PO 4) 3 , where M V = Nb, Ta; M iii = Al, Cr, Fe were examined to obtained a NASICON phase possessing intrinsic conducting properties similar to LiTi 2 (PO 4) 3 but without Ti iv [6]. The planetary mono mill is a technique that uses a high energy ball mill for synthesizing solid electrolyte materials to achieve phase homogeneity of the final product. However, the use of this milling machine is a well-known technique and has attracted the interest of

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A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy

Cited by 75 publications

References 48 publications

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

High Lithium-Ion-Conducting NASICON-Type Li1+xAlxGeyTi2−x−y(PO4)3 Solid Electrolyte

Physical characterization and electrical conductivity of Li1.2Ti1.8Al0.2(PO4)3 and Li1.2Ta0.9Al1.1(PO4)3 NASICON material

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A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy

Cited by 75 publications

References 48 publications

Very fast bulk Li ion diffusivity in crystalline Li1.5Al0.5Ti1.5(PO4)3as seen using NMR relaxometry

Very fast bulk Li ion diffusivity in crystalline Li1.5Al0.5Ti1.5(PO4)3as seen using NMR relaxometry

High Lithium-Ion-Conducting NASICON-Type Li1+xAlxGeyTi2−x−y(PO4)3 Solid Electrolyte

Physical characterization and electrical conductivity of Li1.2Ti1.8Al0.2(PO4)3 and Li1.2Ta0.9Al1.1(PO4)3 NASICON material

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Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry