arXiv subjects

Harald Schmidt

Publications and source records attributed to Harald Schmidt.

5 recordsLinked to original sources

arXiv2026

Operando Characterization of Volume Changes in Lithium-Ion Battery Electrodes during Cycling using Isotope Multilayers

This study reports on advancements in operando characterization of volume changes in lithium-ion battery (LIB) electrode materials during electrochemical cycling. Volume changes are crucial for LIB operation because they are related to the amount of stored energy as well as LIB integrity, performance, and safety. The study introduces a method based on isotope multilayers as active material to track the intrinsic modification of electrode volume in real time under operating conditions with operando neutron reflectometry. A natGe-73Ge multilayer film is used as a model system to measure the volume change of amorphous germanium electrodes during charging and discharging. Isotope modulation produces a Bragg peak in the neutron reflectivity pattern, sensitive only to the modification of volume within the active material of the electrode. Battery side reactions, such as the growth and reduction of the solid-electrolyte interphase is excluded. Using this method, the volume modification as a function of Li content x in LixGe can easily be derived from the scattering vector position of the Bragg peak without fitting numerous complex reflectivity patterns. The experiments show a reversible volume change of amorphous germanium of up to 250 percent for x = 3, which appears to be largely independent of current density, cycle number, and the thickness of the individual Ge layers. Also, there are tentative indications that the crystallization and re-amorphization of LixGe are not influencing the volume change.

cond-mat.mtrl-sci↗

arXiv2025

Hydrogen response to high-density dislocations in bulk perovskite oxide SrTiO3

Hydrogen plays an increasingly important role in green energy technologies. For instance, proton-conducting oxides with high performance for fuel cell components or electrolysers need to be developed. However, this requires a fundamental understanding of hydrogen-defects interactions. While point defects and grain boundaries in oxides have been extensively studied, the role of dislocations as line defects remains less understood, primarily due to the challenge for effective dislocation engineering in brittle oxides. In this work, we demonstrate the impact of dislocations in bulk single-crystal perovskite oxide SrTiO3 on hydrogen uptake and diffusion using deuterium as tracer. Dislocations with a high density up to ~10 to the power of 14 per square meter were mechanically introduced at room temperature. Exposing this dislocation-rich and the reference regions (with a dislocation density of ~10 to the power of 10 per square meter) to deuterium at 400 {\deg}C for 1h, followed by secondary ion mass spectrometry measurements, we observed a ~100 times increase in deuterium incorporation in the dislocation-rich region. The result suggests that dislocations in oxides can act as an effective reservoir for deuterium. This proof-of-concept brings new insights into the emerging hydrogen-dislocation interactions in functional oxides.

cond-mat.mtrl-sci↗

arXiv2025

The meaning of Li diffusion in cathode materials for the cycling of Li-ion batteries: A case study on LiNi0.33Mn0.33Co0.33O2 thin films

We demonstrate that for polycrystalline LiNi0.33Mn0.33Co0.33O2 c-axis textured thin film cathodes of rechargeable lithium-ion batteries, the kinetics of Li storage and release including maximum specific capacity is determined by Li diffusion. The C-rate capability and long-term cycling behavior were investigated. The films exhibited up to 30% of the expected practical capacity even at low C-rates. However, 100% capacity was achieved at very low cycling rates below 0.01C. The capacity showed a reversible behaviour with changing current density, indicating no film degradation. The C-rate capability experiment showed a square root dependence of capacities on current density, which corresponds to a diffusion-controlled process. The estimated diffusivities from the cycling experiments are independent of the current density. The Li chemical and tracer diffusivities were measured using standard electrochemical and non-electrochemical diffusion measurement techniques. Chemical diffusivities, thermodynamic factor, and hence Li tracer diffusivities were determined from potentiostatic intermittent titration (PITT) and electrochemical impedance spectroscopy (EIS) experiments as a function of electrode potential and state of charge (SOC). The diffusivities were found to be approximately independent of potential, SOC and cycle number. The Li tracer diffusivities were validated by 6Li tracer diffusion experiments with secondary ion mass spectrometry (SIMS). The diffusivities obtained by PITT and SIMS were found to be more reliable for Li uptake and release than those obtained by EIS. Based on the diffusion results, a C-rate limit for full film delithiation below 0.01 C was calculated due to slow Li diffusion.

cond-mat.mtrl-sci↗

arXiv2024

Ferroelectric to paraelectric structural transition in LiTaO$_3$ and LiNbO$_3$

The ferroelectric to paraelectric phase transition in LiTaO$_3$ and in pure as well as Mg doped LiNbO$_3$ is investigated theoretically by atomistic calculations in the framework of the density functional theory, as well as experimentally by calorimetry and electrical conductivity measurements. First principles models within the stochastic self-consistent harmonic approximation (SSCHA) allow to consider anharmonic effects and thus to obtain a realistic estimate of the Curie temperature $T_C$ of both ferroelectrics. \textit{Ab initio} molecular dynamics (AIMD) calculations performed on large supercells confirm the Curie temperatures estimated with the SSCHA approach. Moreover, they also suggest that the structural phase transition is a continuous process beginning at temperatures well below $T_C$. According to AIMD, significant ionic displacements occurr already at temperatures of about 100\,K and 300\,K below $T_C$ in LiTaO$_3$ and LiNbO$_3$, respectively. To asses whether and how far the ionic displacements affect the materials properties, the AIMD results are compared with measurements of the electrical conductivity and of the heat capacity across the phase transition. Our first principles calculations moreover show that Mg ions, a frequently employed dopant, raise the Curie temperature in LiNbO$_3$.

cond-mat.mtrl-sci↗

arXiv2020

Do Black and Indigenous Communities Receive their Fair Share of Vaccines Under the 2018 CDC Guidelines

A major focus of debate about rationing guidelines for COVID-19 vaccines is whether and how to prioritize access for minority populations that have been particularly affected by the pandemic, and been the subject of historical and structural disadvantage, particularly Black and Indigenous individuals. We simulate the 2018 CDC Vaccine Allocation guidelines using data from the American Community Survey under different assumptions on total vaccine supply. Black and Indigenous individuals combined receive a higher share of vaccines compared to their population share for all assumptions on total vaccine supply. However, their vaccine share under the 2018 CDC guidelines is considerably lower than their share of COVID-19 deaths and age-adjusted deaths. We then simulate one method to incorporate disadvantage in vaccine allocation via a reserve system. In a reserve system, units are placed into categories and units reserved for a category give preferential treatment to individuals from that category. Using the Area Deprivation Index (ADI) as a proxy for disadvantage, we show that a 40% high-ADI reserve increases the number of vaccines allocated to Black or Indigenous individuals, with a share that approaches their COVID-19 death share when there are about 75 million units. Our findings illustrate that whether an allocation is equitable depends crucially on the benchmark and highlight the importance of considering the expected distribution of outcomes from implementing vaccine allocation guidelines.

econ.GN↗