Ion-conducting glass-ceramics for energy-storage applications

Eckert, Hellmut; Rodrigues, Ana Cândida Martins

doi:10.1557/mrs.2017.30

Cited by 32 publications

(58 citation statements)

References 63 publications

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“…From the X‐ray powder patterns, one can see that substitution of Ge 4+ by Ga 3+ and Sc 3+ was successful, although in the latter case a multiphase crystallization pattern was observed in the DSC analysis for LSGP precursor glass and some extra peaks were also observed in the diffraction pattern. As previously shown, the exact degree of Ge substitution x in the NASICON phase can be obtained from the 31 P MAS‐NMR spectra using the expression

\frac{M^{3 +}}{{Ge}^{4 +}} = \frac{4 I_{4} + 3 I_{3} + 2 I_{2} + I_{1}}{I_{3} + 2 I_{2} + 3 I_{1} + 4 I_{0}} = \frac{x}{2 - x},

where I n refers to the fractional area of each P 4 (4‐n)Ge,nM signal component. Using the data shown in Table , values of x = 0.53 and 0.38 are calculated for LGGP‐C‐606 and LSGP‐C‐690, respectively.…”

Section: Discussionmentioning

confidence: 99%

“…Lithium‐ion batteries played such an important role in the technological revolution that took place in the past two decades that their developers received the 2019 Nobel Prize in Chemistry . To date, commercial lithium‐ion batteries employ liquid‐organic electrolytes which present both operational drawbacks like restricted cyclability (due to electrode corrosion) and health hazards caused by leakage of the electrode . All‐solid‐state batteries are believed to be the next step in the evolution of batteries as they avoid such drawbacks .…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, optimized solid‐state electrolytes with high ionic conductivity are required. One of the most promising solid electrolyte systems found in the literature is based on glass‐ceramics in the Na‐Super Ionic Conductor (NASICON) phase field . The first NASICON glass‐ceramic systems were reported and patented by J. Fu in 1997 .…”

Section: Introductionmentioning

confidence: 99%

“…Li + ions can occupy two sites named M1 (sixfold coordinated located between MO 6 octahedra) and M2 (eightfold coordinated and located between two MO 6 columns). In the LiGe 2 (PO 4 ) 3 parent compound, the M1 sites are fully occupied while the M2 sites are vacant, and at elevated temperatures, ionic transport occurs by hopping between these sites . To improve the ionic conduction, aliovalent substitution of M 4+ by Mʹ 3+ ions having slightly larger ionic radii than M 4+ can be employed.…”

Section: Introductionmentioning

confidence: 99%

“…This procedure widens the bottleneck window between the two sites and introduces additional Li + ions in the NASICON structure for charge compensation, which can be accommodated at the M2 sites. At higher x contents, a redistribution of populations takes place …”

Section: Introductionmentioning

confidence: 99%

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Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Silva¹,

Nieto‐Muñoz

Rodrigues

et al. 2020

J Am Ceram Soc

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This work reports structural and lithium-ion mobility studies in NASICON singleor multiple phase Li 1+x M x Ge 2−x (PO 4 ) 3 (M = Ga 3+ , Sc 3+ , Y 3+ ) glass-ceramics using solid-state NMR techniques, X-ray powder diffraction, and impedance spectroscopy. X-ray powder diffraction data show the successful incorporation of Ga 3+ and Sc 3+into the Ge 4+ octahedral sites of the NASICON structure at the levels of x = 0.5 and 0.4, respectively. The glass-to-crystal transition was further characterized by multinuclear NMR and electrical conductivity measurements. Among the studied samples, the gallium-containing glass-ceramic presented the highest DC conductivity, 1.1 × 10 −4 S/cm at room temperature, whereas for the Sc-containing samples, the maximum room temperature conductivity that could be reached was 4.8 × 10 −6 S/ cm. No indications of any substitution of Ge 4+ by Y 3+ could be found. K E Y W O R D S ionic conductivity, nuclear magnetic resonance, phosphates, structure How to cite this article: d'Anciães Almeida Silva I, Nieto-Muñoz AM, Rodrigues ACM, Eckert H. Structure and lithium-ion mobility in Li 1.5 M 0.5 Ge 1.5 (PO 4 ) 3 (M = Ga, Sc, Y) NASICON glass-ceramics. J Am Ceram Soc. 2020;103:4002-4012. https ://doi.

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