arXiv subjects

B. Roling

Publications and source records attributed to B. Roling.

6 recordsLinked to original sources

arXiv2017

Superionic diffusion through frustrated energy landscape

Solid-state materials with high ionic conduction are necessary to many technologies including all-solid-state Li-ion batteries. Understanding how crystal structure dictates ionic diffusion is at the root of the development of fast ionic conductors. Here, we show that LiTi2(PS4)3 exhibits a Li-ion diffusion coefficient about an order of magnitude higher than current state-of-the-art lithium superionic conductors. We rationalize this observation by the unusual crystal structure of LiTi2(PS4)3 which offers no regular tetrahedral or octahedral sites for lithium to favorably occupy. This creates a smooth, frustrated energy landscape resembling more the energy landscapes present in liquids than in typical solids. This frustrated energy landscape leads to a high diffusion coefficient combining low activation energy with a high pre-factor.

cond-mat.mtrl-sci↗

arXiv2009

Electrode Polarization in Glassy Electrolytes: Large Interfacial Capacitance Values and Indication for Pseudocapacitive Charge Storage

We study the electrode polarization behaviour of different Na-Ca-phosphosilicate glasses by measuring the differential capacitance between blocking Pt electrodes. At low applied dc bias voltages, we detect a linear capacitance regime with interfacial capacitance values considerably larger than expected from double layer theories and also considerably larger than found for ionic liquids with similar ion concentrations. With increasing bias voltages, the differential capacitance of interfacial layer exhibits a maximum around 1 V and a strong drop at higher voltages. We suggest that these features are caused by pseudocapacitive processes, namely by the adsorption of mobile Na+ ions at the electrodes followed by electronic charge transfer. While pseudocapacitive processes are well known in liquid electrochemistry, more detailed studies on solid electrolytes should offer perspectives for improved energy storage in solid-state supercapacitors

cond-mat.dis-nn↗

arXiv2008

Mechanism and Kinetics of Na+ Ion Depletion under the Anode during Electro-thermal Poling of a Bioactive Glass

Electro-thermal poling experiments were carried out on a bioactive glass, and the kinetics of the Na+ ion depletion layer formation under the anode was studied in-situ by means of ac impedance spectroscopy. One important finding is a linear relation between the depletion layer thickness and the applied voltage, which is in contrast to the predictions of standard space charge theory. The average electric field in the layer is independent of the voltage and is close to the dielectric breakdown field of alkali ion conducting glasses. Furthermore, we observe that the thickness of the depletion layer is established on a much shorter time scale than the resistance. We explain these results by assuming that the huge electric fields created under the anode during Na+ ion depletion lead to a strong increase of the electronic mobility in the layer and to charge compensation via extraction of electrons. It is shown that in the initial stages of the depletion process, a relative Na+ ion depletion of only 400 ppm is sufficient to generate electric fields of the order of the dielectric breakdown field.

cond-mat.mtrl-sci↗

arXiv2007

Investigation of Bioglass-Electrode Interfaces after Thermal Poling

Electrical and electrochemical processes in a bioactive soda-lime phosphosilicate glasses and in a bioabsorbable soda-lime phosphate glass during thermal poling were studied by means of thermally stimulated depolarization current measurements, ac impedance spectroscopy, and SEM/EDX analyses. The thermal poling was done by sputtering thin Pt electrode films onto the faces of the glass samples and by applying voltages up to 1 kV to the electrodes at temperatures up to 513 K. The poling leads to the formation of interfacial layers under the electrodes which are responsible for two depolarization current peaks and for one additional semicircle in a Nyquist plot of the ac impedance. The SEM/EDX profiles suggest that redox and transport processes of Na+ ions are responsible for the formation of the interfacial layers and that Ca2+ ions are immobile under the poling conditions. The sodium depletion layer under the anode leads to a negative surface charge of the glass samples which may enhance their bioactivity.

cond-mat.mtrl-sci↗

arXiv2004

Application of Nonlinear Conductivity Spectroscopy to Ion Transport in Solid Electrolytes

The field-dependent ion transport in thin samples of different glasses is characterised by means of nonlinear conductivity spectroscopy. AC electric fields with strengths up to 77 kV/cm are applied to the samples, and the Fourier components of the current spectra are analysed. In the dc conductivity regime and in the transition region to the dispersive conductivity, higher harmonics in the current spectra are detected, which provide information about higher--order conductivity coefficients. Our method ensures that these higher--order conductivity coefficients are exclusively governed by field--dependent ion transport and are not influenced by Joule heating effects. We use the low-field dc conductivity $σ_{1,dc}$ and the higher--order dc conductivity coefficient $σ_{3,dc}$ to calculate apparent jump distances for the mobile ions, $a_{\rm app}$. Over a temperature range from 283 K to 353 K, we obtain values for $a_{app}$ between 39 Å$ $ and 55 Å. For all glasses, we find a weak decrease of $a_{\rm app}$ with increasing temperature. Remarkably, the apparent jump distances calculated from our data are considerably larger than typical values published in the literature for various ion conducting glasses. These values were obtained by applying dc electric fields. Our results provide clear evidence that the equation used in the literature to calculate the apparent jump distances does not provide an adequate physical description of field-dependent ion transport.

cond-mat.mtrl-sci↗

arXiv2004

Probing ion transport at the nanoscale: Time-domain electrostatic force spectroscopy on glassy electrolytes

We have carried out time--domain electrostatic force spectroscopy on two different ion conducting glasses using an atomic force microscope. We compare the electrostatic force spectroscopic data obtained at different temperatures with macroscopic electrical data of the glasses. The overall consistency of the data shows that electrostatic force spectroscopy is capable of probing the ion dynamics and transport in nanoscopic subvolumes of the samples.

cond-mat.mtrl-sci↗