Structural analysis and electrical characterization of cation-substituted lithium ion conductors Li1−Ti1−MOPO4 (M = Nb, Ta, Sb)

Hofmann, Patrick; Ariai, Jama; Zaichenko, Aleksandr; Janek, Jürgen; Mollenhauer, Doreen; Zeier, Wolfgang G.

doi:10.1016/j.ssi.2018.01.049

Cited by 4 publications

(3 citation statements)

References 40 publications

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“…In situ synchrotron XRD measurements were then carried out on each mixture (in air) while heating at a rate of 25°C/min to 700°C, followed by a 3-hour hold at this temperature. The selected precursors and conditions were chosen based on previous work where LTOPO was synthesized (26,27,(30)(31)(32). The phosphate source was changed to vary the reactivity of the starting precursor mixture, which we will show has a prominent effect on the resulting synthesis pathway and product selectivity.…”

Section: In Situ Characterization Of Ltopo Synthesismentioning

confidence: 99%

Selective formation of metastable polymorphs in solid-state synthesis

Zeng,

Szymanski,

et al. 2024

Sci. Adv.

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Metastable polymorphs often result from the interplay between thermodynamics and kinetics. Despite advances in predictive synthesis for solution-based techniques, there remains a lack of methods to design solid-state reactions targeting metastable materials. Here, we introduce a theoretical framework to predict and control polymorph selectivity in solid-state reactions. This framework presents reaction energy as a rarely used handle for polymorph selection, which influences the role of surface energy in promoting the nucleation of metastable phases. Through in situ characterization and density functional theory calculations on two distinct synthesis pathways targeting LiTiOPO 4 , we demonstrate how precursor selection and its effect on reaction energy can effectively be used to control which polymorph is obtained from solid-state synthesis. A general approach is outlined to quantify the conditions under which metastable polymorphs are experimentally accessible. With comparison to historical data, this approach suggests that using appropriate precursors could enable targeted materials synthesis across diverse chemistries through selective polymorph nucleation.

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Section: In Situ Characterization Of Ltopo Synthesismentioning

confidence: 99%

Selective formation of metastable polymorphs in solid-state synthesis

Zeng,

Szymanski,

et al. 2024

Sci. Adv.

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“…This is particularly important when small energetic differences occur. To characterize the transport properties of LIPON structures, the activation energy is mainly compared with experimental data and used to determine the ionic conductivity 16,23,24 . The activation energy is composed of the migration energy (kinetic barrier) of the respective diffusion path and the Frenkel pair energy (thermodynamic factor), which accounts for the formation of vacancies and interstitial ions.…”

Section: Introductionmentioning

confidence: 99%

“…To characterize the transport properties of LIPON structures, the activation energy is mainly compared with experimental data and used to determine the ionic conductivity. 16,23,24 The activation energy is composed of the migration energy (kinetic barrier) of the respective diffusion path and the Frenkel pair energy (thermodynamic factor), which accounts for the formation of vacancies and interstitial ions. The primary exchange-correlation (XC) functionals used to study LIPON or solid-state structures in general (without transition state atoms) are the local-density approximation (LDA) functional and the generalized gradient approximation (GGA) functional from Perdew, Burke, and Ernzerhof (PBE).…”

mentioning

confidence: 99%

Uncertainty of exchange‐correlation functionals in density functional theory calculations for lithium‐based solid electrolytes on the case study of lithium phosphorus oxynitride

Henkel

Mollenhauer

2021

J Comput Chem

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Amorphous lithium phosphorus oxynitride (LIPON) has emerged as a promising solid electrolyte for all-solid-state thin-film lithium batteries. In this context, the use of theoretical modeling to characterize, understand, or screen material properties is becoming increasingly important to complement experimental analysis or elucidate features at atomistic level that are difficult to obtain through experimental studies. Density functional theory (DFT) is the method of choice for quantum mechanical material modeling at the atomistic scale. The current state of the art represents DFT values, such as the formation or migration energies relevant for bulk phase of materials, as absolute numbers. Estimating the accuracy or fluctuation range of the different density functionals is challenging. In order to investigate the thermodynamic and kinetic properties of LIPON by DFT, an approach to describe the fluctuation range caused by the choice of the exchange-correlation (XC) functional is developed. Three different model systems were chosen to characterize various structural features of amorphous LIPON, which are distinguished by the cross-linking of the PO u N 4-u -structural units. The uncertainty Ũ is introduced as a parameter describing the fluctuation range of energy values. The uncertainty approach does not determine the accuracy of DFT results, but rather a fluctuation range in the DFT results without the need for a reference value from a higher level of theory or experiment. The uncertainty was determined for both the thermodynamic Li-vacancy formation energies and the kinetic Li-vacancy migration energies in LIPON. We assume that the uncertainty approach can be applied to different material systems with different density functionals.

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On the way to understand the keys for the stabilization of the conductive phase in doped- NASICON-type materials

Terny

López

Narda

et al. 2022

Ceramics International

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Structural analysis and electrical characterization of cation-substituted lithium ion conductors Li1−Ti1−MOPO4 (M = Nb, Ta, Sb)

Cited by 4 publications

References 40 publications

Selective formation of metastable polymorphs in solid-state synthesis

Selective formation of metastable polymorphs in solid-state synthesis

Uncertainty of exchange‐correlation functionals in density functional theory calculations for lithium‐based solid electrolytes on the case study of lithium phosphorus oxynitride

On the way to understand the keys for the stabilization of the conductive phase in doped- NASICON-type materials

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Structural analysis and electrical characterization of cation-substituted lithium ion conductors Li1−Ti1−MOPO4 (M = Nb, Ta, Sb)

Cited by 4 publications

References 40 publications

Selective formation of metastable polymorphs in solid-state synthesis

Selective formation of metastable polymorphs in solid-state synthesis

Uncertainty of exchange‐correlation functionals in density functional theory calculations for lithium‐based solid electrolytes on the case study of lithium phosphorus oxynitride

On the way to understand the keys for the stabilization of the conductive phase in doped- NASICON-type materials

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Structural analysis and electrical characterization of cation-substituted lithium ion conductors Li1−Ti1−MOPO4 (M = Nb, Ta, Sb)