Lithium Mobility in Borate and Phosphate Glass Networks

Welsch, Anna-Maria; Behrens, Harald; Murawski, Dawid; Horn, I.

doi:10.1515/zpch-2016-0927

Cited by 9 publications

(6 citation statements)

References 37 publications

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“…The presence of an AlPO

secondary phase, for example, has been shown to significantly affect the LATP performance [ 72 ]. Similarly, Welsch et al [ 74 ] have recently found a significantly lowered Li

mobility in Li-Mg-phosphate glass networks. While this particular T

stoichiometry studied herein is thus not a viable candidate for interfacial engineering, other possible compositions in the multidimensional phase space may exhibit less drastic effects.…”

Section: Resultsmentioning

confidence: 73%

Exploiting Nanoscale Complexion in LATP Solid-State Electrolyte via Interfacial Mg2+ Doping

2022

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While great effort has been focused on bulk material design for high-performance All Solid-State Batteries (ASSBs), solid-solid interfaces, which typically extend over a nanometer regime, have been identified to severely impact cell performance. Major challenges are Li dendrite penetration along the grain boundary network of the Solid-State Electrolyte (SSE) and reductive decomposition at the electrolyte/electrode interface. A naturally forming nanoscale complexion encapsulating ceramic Li1+xAlxTi2−x(PO4)3 (LATP) SSE grains has been shown to serve as a thin protective layer against such degradation mechanisms. To further exploit this feature, we study the interfacial doping of divalent Mg2+ into LATP grain boundaries. Molecular Dynamics simulations for a realistic atomistic model of the grain boundary reveal Mg2+ to be an eligible dopant candidate as it rarely passes through the complexion and thus does not degrade the bulk electrolyte performance. Tuning the interphase stoichiometry promotes the suppression of reductive degradation mechanisms by lowering the Ti4+ content while simultaneously increasing the local Li+ conductivity. The Mg2+ doping investigated in this work identifies a promising route towards active interfacial engineering at the nanoscale from a computational perspective.

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“…The presence of an AlPO

secondary phase, for example, has been shown to significantly affect the LATP performance [ 72 ]. Similarly, Welsch et al [ 74 ] have recently found a significantly lowered Li

mobility in Li-Mg-phosphate glass networks. While this particular T

stoichiometry studied herein is thus not a viable candidate for interfacial engineering, other possible compositions in the multidimensional phase space may exhibit less drastic effects.…”

Section: Resultsmentioning

confidence: 73%

Exploiting Nanoscale Complexion in LATP Solid-State Electrolyte via Interfacial Mg2+ Doping

2022

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“…As a model system we have chosen lithium borate, for which the structure -transport relation has already attracted a considerable amount of attention. [12][13][14][15][16][17][18] We describe the results of unique transport experiments, where native mobile lithium ions in a lithium borate glass are depleted and replaced uni-directionally by foreign alkali ions M + = K + , Rb + and Cs + in a charge attachment induced transport (CAIT) experiment. The resulting depletion/replacement profiles extend down to several hundred nm into the material as measured by time-of-flight secondary ion mass spectrometry (ToF-SIMS) resembling time-dependent macroscopic transport with characteristic transport coefficients.…”

Section: Introductionmentioning

confidence: 99%

Manifestation of site energy landscapes for ion transport in borate glasses

Gunawan,

Schäfer,

Weitzel

2024

Phys. Chem. Chem. Phys.

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“…Apart from applications in the field of materials science, it has been demonstrated that -in the realm of Earth sciences -LA depth profile analyses are also suitable to investigate Hf isotope variations, U-Pb ages, and trace element zoning in zircon (Woodhead et al, 2004;Steely et al, 2014;Marsh and Stockli, 2015;Zirakparvar, 2015;Nakazato et al, 2022). Despite the widespread use of LA multicollector ICP-MS (LA-MC-ICP-MS) systems for spatially resolved measurements of radiogenic and stable isotopic compositions of geomaterials -for an overview of recent advances see, e.g., Degryse and Vanhaecke (2016), Woodhead et al (2016), and Balaram et al (2022) -studies of laser-based depth profile analyses of metal stable isotopes have, to our knowledge, not yet been conducted, except for Li isotope diffusion profiles in experimental Li phosphate glasses (Welsch et al, 2017). Femtosecond laser ablation systems coupled to a MC-ICP-MS instrument should be particularly suitable for such depth analyses, as it has been demonstrated that femtosecond laser ablation (fs-LA) is capable of sampling a variety of minerals stoichiometrically (d'Abzac et al, 2013(d'Abzac et al, , 2014Zheng et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

Oeser,

Horn,

Dohmen

et al. 2023

Eur. J. Mineral.

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Abstract. Femtosecond laser ablation (fs-LA) coupled to a multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) instrument has been proven to be a powerful means to analyze isotope ratios of “non-traditional” stable isotope systems with high spatial resolution, precision, and accuracy. The technique has been successfully applied, e.g., to investigate diffusion-generated isotopic zoning of the elements Li, Mg, and Fe in magmatic crystals. Here, we present a novel sampling technique employing a fs-LA system that is equipped with a computer numerical control (CNC) laser stage, using the open-source software LinuxCNC. Combining this laser set up with ICP-MS or MC-ICP-MS allows us to perform depth profile analyses of major and trace elements, respectively, as well as metal stable isotope variations of Fe and Mg in olivine crystals and in experimental diffusion couples. Samples are ablated in circular patterns with profile diameters of 100–200 µm using a laser spot size of 25–30 µm. Depending on the scan speed and the repetition rate of the laser, each ablated sample layer is between 300 nm and 3.0 µm thick. The integrated signal of one ablated layer represents one data point of the depth profile. We have tested this technique by analyzing 5–50 µm deep depth profiles (consisting of 15–25 individual layers) of homogeneous and chemically zoned olivine crystal cuboids. The minor and trace element analyses of the zoned cuboids, conducted by fs-LA-ICP-MS, were compared with “horizontal” profiles analyzed in polished sections of the cuboids with electron probe microanalysis (EPMA). Furthermore, we analyzed Fe–Mg isotopic depth profiles of the same cuboids with fs-LA-MC-ICP-MS, of which the chemically zoned ones also showed isotopic zoning at identical scales. Isotopic depth profiles were also conducted on an unzoned olivine cuboid that was coated with a 26Mg- and 56Fe-enriched olivine thin film (of ∼ 800 nm) in order to investigate top-to-bottom contamination during depth profiling. Our results indicate that (i) concentration data acquired by fs-LA depth profiling match well with EPMA data, (ii) precise and accurate Fe and Mg isotopic data can be obtained (i.e., precision and accuracy are ≤ 0.12 ‰ and ≤ 0.15 ‰ for both δ26Mg and δ56Fe, respectively), and (iii) potential top-to-bottom contamination during depth profiling of isotope ratios can be avoided. The technique presented herein is particularly suitable for the investigation of minerals or glasses with chemical and/or isotopic gradients (e.g., diffusion zoning) vertical to planar surfaces. It can also be applied in materials sciences in order to analyze thin films, coatings, or surface contaminations on solids.

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Lithium Mobility in Borate and Phosphate Glass Networks

Abstract: In order to improve our understanding of the Li-mobility in oxide glass networks with Li as the principle mobile particle, electrical conductivity and self-diffusivity of lithium was studied in two phosphate (0.2 Li

Cited by 9 publications

References 37 publications

Exploiting Nanoscale Complexion in LATP Solid-State Electrolyte via Interfacial Mg2+ Doping

Exploiting Nanoscale Complexion in LATP Solid-State Electrolyte via Interfacial Mg2+ Doping

Manifestation of site energy landscapes for ion transport in borate glasses

Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

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