High-Frequency Conductivity Plateau and Ionic Hopping Processes in a Ternary Lithium Borate Glass

Complete conductivity spectra of a lithium ion conducting glass of composition B2O3-0.56Li2O - 0.45 LiBr have been taken at twelve temperatures from 173 K to 573 K, covering the frequency range from a few Hertz up to about 50 THz. For the first time, a separation of the hopping and vibrational contributions to the spectra has been performed. The resulting frequency dependent hopping conductivity displays a high-frequency plateau similar to those known to exist in crystalline solid electrolytes like RbAg4I5 and Na-β-alumina. In the dispersive regime of the conductivity, there is an increase of the apparent power-law exponent from p = 0.6 to q = 1.3. The spectra are evaluated by combined application of the jump relaxation model and the dynamic structure model. Besides the translational hopping of the lithium ions via the preferred Ā sites, more localized kinds of motion are also detected, viz., hops into the less favoured C̄ sites (and mostly back again) as well as smaller displacements of the ions within their local environment.

Download Full-text

Complete Conductivity Spectra of Crystalline and Glassy Fast Ion Conductors Up to Far Infrared Frequencies

MRS Proceedings ◽

10.1557/proc-369-233 ◽

1994 ◽

Vol 369 ◽

Cited By ~ 9

Author(s):

C. Cramer ◽

R. Graeber ◽

M.D. Ingram ◽

T. Saatkamp ◽

D. Wilmer ◽

...

Keyword(s):

High Frequency ◽

Lithium Ion ◽

Dynamic Structure ◽

Far Infrared ◽

Crystalline Solid ◽

Relaxation Model ◽

Combined Application ◽

Ion Conducting ◽

Infrared Frequencies ◽

Conductivity Spectra

AbstractComplete conductivity spectra have been taken of a lithium ion conducting glass of composition B2O3 · 0.56Li2O · 0.45LiBr and of lithium stabilized Na-β″-alumina, at various temperatures. — In the glass, it has forthe first time been possible to separate the hopping and vibrational contributions to theconductivity. The resulting hopping conductivity spectra display high-frequency plateaux similar to those known to exist in crystalline solid electrolytes like RbAg415 and Na-β-alumina. In the dispersive regime, the spectra are characterized bytwo different power-law exponents, p = 0.6 and q = 1.3. The data are evaluated by combined application of the jump relaxation model and the dynamic structure model. — Na-β″-alumina has pronounced high-frequency plateaux between about 200 GHz and 400 GHz. The hopping observed in the spectra can be decomposed into hops that are a priori unsuccessful and others that can be treated in terms of the jump relaxation model. The latter fraction is found to increase with increasing temperature.

Download Full-text

Atomic Layer Deposition of LiF and Lithium Ion Conducting (AlF3)(LiF)x Alloys Using Trimethylaluminum, Lithium Hexamethyldisilazide and Hydrogen Fluoride

10.26434/chemrxiv.5459653 ◽

2017 ◽

Author(s):

Younghee Lee ◽

Daniela M. Piper ◽

Andrew S. Cavanagh ◽

Matthias J. Young ◽

Se-Hee Lee ◽

...

Keyword(s):

Lithium Ion ◽

Atomic Layer ◽

Mass Gain ◽

Alloy Film ◽

Ex Situ ◽

X Ray ◽

Layer Deposition ◽

Ion Conducting ◽

Good Agreement

<div>Atomic layer deposition (ALD) of LiF and lithium ion conducting (AlF3)(LiF)x alloys was developed using trimethylaluminum, lithium hexamethyldisilazide (LiHMDS) and hydrogen fluoride derived from HF-pyridine solution. ALD of LiF was studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectrometer (QMS) at reaction temperatures between 125°C and 250°C. A mass gain per cycle of 12 ng/(cm2 cycle) was obtained from QCM measurements at 150°C and decreased at higher temperatures. QMS detected FSi(CH3)3 as a reaction byproduct instead of HMDS at 150°C. LiF ALD showed self-limiting behavior. Ex situ measurements using X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) showed a growth rate of 0.5-0.6 Å/cycle, in good agreement with the in situ QCM measurements.</div><div>ALD of lithium ion conducting (AlF3)(LiF)x alloys was also demonstrated using in situ QCM and in situ QMS at reaction temperatures at 150°C A mass gain per sequence of 22 ng/(cm2 cycle) was obtained from QCM measurements at 150°C. Ex situ measurements using XRR and SE showed a linear growth rate of 0.9 Å/sequence, in good agreement with the in situ QCM measurements. Stoichiometry between AlF3 and LiF by QCM experiment was calculated to 1:2.8. XPS showed LiF film consist of lithium and fluorine. XPS also showed (AlF3)(LiF)x alloy consists of aluminum, lithium and fluorine. Carbon, oxygen, and nitrogen impurities were both below the detection limit of XPS. Grazing incidence X-ray diffraction (GIXRD) observed that LiF and (AlF3)(LiF)x alloy film have crystalline structures. Inductively coupled plasma mass spectrometry (ICP-MS) and ionic chromatography revealed atomic ratio of Li:F=1:1.1 and Al:Li:F=1:2.7: 5.4 for (AlF3)(LiF)x alloy film. These atomic ratios were consistent with the calculation from QCM experiments. Finally, lithium ion conductivity (AlF3)(LiF)x alloy film was measured as σ = 7.5 × 10-6 S/cm.</div>

Download Full-text

Ultrathin Yet Robust Single Lithium‐Ion Conducting Quasi‐Solid‐State Polymer‐Brush Electrolytes Enable Ultralong‐Life and Dendrite‐Free Lithium‐Metal Batteries

Advanced Materials ◽

10.1002/adma.202100943 ◽

2021 ◽

pp. 2100943

Author(s):

Minghong Zhou ◽

Ruliang Liu ◽

Danyang Jia ◽

Yin Cui ◽

Qiantong Liu ◽

...

Keyword(s):

Solid State ◽

Polymer Brush ◽

Lithium Ion ◽

Lithium Metal ◽

Lithium Metal Batteries ◽

Ion Conducting

Download Full-text

Hearing from the ocean and into the river: the evolution of the inner ear of Platanistoidea (Cetacea: Odontoceti)

Paleobiology ◽

10.1017/pab.2021.11 ◽

2021 ◽

pp. 1-21

Author(s):

Mariana Viglino ◽

Maximiliano Gaetán ◽

Mónica R. Buono ◽

R. Ewan Fordyce ◽

Travis Park

Keyword(s):

Inner Ear ◽

High Frequency ◽

Sound Production ◽

Marine Species ◽

Late Oligocene ◽

Evolutionary Patterns ◽

Ear Morphology ◽

Cochlear Morphology ◽

First Time ◽

Hearing Abilities

Abstract The inner ear of the two higher clades of modern cetaceans (Neoceti) is highly adapted for hearing infrasonic (mysticetes) or ultrasonic (odontocetes) frequencies. Within odontocetes, Platanistoidea comprises a single extant riverine representative, Platanista gangetica, and a diversity of mainly extinct marine species from the late Oligocene onward. Recent studies drawing on features including the disparate tympanoperiotic have not yet provided a consensus phylogenetic hypothesis for platanistoids. Further, cochlear morphology and evolutionary patterns have never been reported. Here, we describe for the first time the inner ear morphology of late Oligocene–early Miocene extinct marine platanistoids and their evolutionary patterns. We initially hypothesized that extinct marine platanistoids lacked a specialized inner ear like P. gangetica and thus, their morphology and inferred hearing abilities were more similar to those of pelagic odontocetes. Our results reveal there is no “typical” platanistoid cochlear type, as the group displays a disparate range of cochlear anatomies, but all are consistent with high-frequency hearing. Stem odontocete Prosqualodon australis and platanistoid Otekaikea huata present a tympanal recess in their cochlea, of yet uncertain function in the hearing mechanism in cetaceans. The more basal morphology of Aondelphis talen indicates it had lower high-frequency hearing than other platanistoids. Finally, Platanista has the most derived cochlear morphology, adding to evidence that it is an outlier within the group and consistent with a >9-Myr-long separation from its sister genus Zarhachis. The evolution of a singular sound production morphology within Platanistidae may have facilitated the survival of Platanista to the present day.

Download Full-text

Synthesis of Lithium-ion Conducting Polymers Designed by Machine Learning-based Prediction and Screening

Chemistry Letters ◽

10.1246/cl.180847 ◽

2019 ◽

Vol 48 (2) ◽

pp. 130-132 ◽

Cited By ~ 9

Author(s):

Kan Hatakeyama-Sato ◽

Toshiki Tezuka ◽

Yoshinori Nishikitani ◽

Hiroyuki Nishide ◽

Kenichi Oyaizu

Keyword(s):

Machine Learning ◽

Conducting Polymers ◽

Lithium Ion ◽

Ion Conducting ◽

Ion Conducting Polymers

Download Full-text

Sodium, Silver and Lithium-Ion Conducting β″-Alumina + YSZ Composites, Ionic Conductivity and Stability

Crystals ◽

10.3390/cryst11030293 ◽

2021 ◽

Vol 11 (3) ◽

pp. 293

Author(s):

Liangzhu Zhu ◽

Anil V. Virkar

Keyword(s):

Ion Exchange ◽

Electrochemical Impedance ◽

Ionic Conductivities ◽

Lithium Ion ◽

Co2 Corrosion ◽

Ionic Conductors ◽

Ion Conductor ◽

Sensor Applications ◽

Potential Applications ◽

Ion Conducting

Na-β″-alumina (Na2O.~6Al2O3) is known to be an excellent sodium ion conductor in battery and sensor applications. In this study we report fabrication of Na- β″-alumina + YSZ dual phase composite to mitigate moisture and CO2 corrosion that otherwise can lead to degradation in pure Na-β″-alumina conductor. Subsequently, we heat-treated the samples in molten AgNO3 and LiNO3 to respectively form Ag-β″-alumina + YSZ and Li-β″-alumina + YSZ to investigate their potential applications in silver- and lithium-ion solid state batteries. Ion exchange fronts were captured via SEM and EDS techniques. Their ionic conductivities were measured using electrochemical impedance spectroscopy. Both ion exchange rates and ionic conductivities of these composite ionic conductors were firstly reported here and measured as a function of ion exchange time and temperature.

Download Full-text