arXiv subjects

Kasper Tolborg

Publications and source records attributed to Kasper Tolborg.

8 recordsLinked to original sources

arXiv2026

Local Structure Dictates Ionic Transport and Mechanical Properties in Glassy Solid Electrolytes for Lithium Batteries

Electrolytes composed of sulfide and halide glasses are promising candidates for all-solid-state lithium batteries owing to their processability, lack of grain boundaries, and relatively high ionic conductivity. Nevertheless, their ionic conductivity and mechanical properties are still not satisfying for the real-world applications. Significant advances in solid electrolytes require a thorough understanding of their microstructures. Here, we reveal the connections among structure, ionic transport properties, and mechanical stability in a series of glassy solid electrolytes by employing molecular dynamics simulations based on a machine learning interatomic potential. Specifically, we explore how the interplay between B-S and P-S networks in glassy Li-S-P-B-I (LSPBI) governs ionic conductivity and deformation behavior. The introduction of P2S5 into a B2S3-based glass induces a critical structural transformation, through which both ionic conductivity and mechanical nano-ductility can be enhanced. For a moderate P2S5 content, incorporated PS4 units depolymerize the rigid boron framework, creating percolative diffusion pathways for fast ionic transport. Concurrently, the flexible P-S-P configurations enable energy dissipation through bond bending, leading to the brittle-to-ductile transition. However, excessive P2S5 increases the fraction of polyphosphates (e.g., P2S6 and P2S7), thereby polymerizing the structural network and ultimately impeding Li+ mobility. Our work thus provides atomistic principles for engineering glass electrolytes with balanced ionic conductivity and mechanical robustness.

cond-mat.mtrl-sci↗

arXiv2026

Fast Isotropic Li-Ion Diffusion in Zeolitic Imidazolate Framework Glass Electrolytes for Batteries

All-solid-state lithium batteries require solid electrolytes that combine rapid room-temperature ion transport with mechanical robustness and interfacial compatibility. Zeolitic imidazolate framework (ZIF) glasses, with ZIFs being a sub-set of metal-organic frameworks, offer an attractive yet relatively underexplored platform because they combine an grainboundary-free and amorphous topology with chemically tunable frameworks. Here, we reveal that structural disorder unlocks fast and isotropic lithium diffusion in ZIF glasses. This is realized by using a machine learning interatomic potential to simulate Li+ transport in crystalline and glassy ZIF-4 and ZIF-62. Structural disorder reduces the activation energy for Li+ migration from ~0.35 eV to 0.16 eV and increases the extrapolated room-temperature diffusion coefficient by more than one order of magnitude for ZIF-4 and nearly sevenfold for ZIF-62. Analyses of non-Gaussian dynamics and van Hove correlation functions reveal that Li+ diffusion in crystalline ZIFs occurs via rare, dynamically heterogeneous hopping events among well-defined cages, whereas Li+ diffusion in glassy ZIFs is more homogeneous, continuous, and Fickian-like, benefiting from a wide distribution of coordination geometries and migration barriers. Li+ diffusion in crystalline ZIFs is strongly anisotropic, reflecting that ordered orientations of imidazolate and benzimidazolate rings impose distinct energy barriers along different crystallographic directions. Upon vitrification, these ring orientations become randomized, and hence, the diffusion of Li+ becomes isotropic or near-isotropic. These findings imply that well-designed metal-organic framework glasses are a promising candidate as high-performance solid-state electrolytes.

cond-mat.mtrl-sci↗

arXiv2026

Defect Tolerance in Trigonal Selenium Photovoltaics

Understanding how point defects fundamentally influence photovoltaic performance remains a central question for emerging wide-band gap absorbers. Trigonal selenium (t-Se) has recently re-emerged as a promising photovoltaic material due to its near-optimal band gap for tandem and indoor applications. Here we quantify defect-assisted Shockley-Read-Hall (SRH) recombination in t-Se using first principles calculations across a large and chemically diverse set of point defects. Our results suggest that t-Se is intrinsically defect tolerant. Despite the presence of multiple deep levels in the gap, recombination via nonradiative multi-phonon emission processes is strongly suppressed by large lattice reorganizations and large energy releases of at least 0.5 EG per recombination event, while radiative defect-assisted capture also remains too small to account for the observed device losses. Consequently, SRH recombination mediated by realistic concentrations of point defects cannot account for the observed efficiency limitations in selenium photovoltaics. We explore trends in both radiative and nonradiative SRH recombination rates across the defect data set, highlighting their complex dependence on defect level position, lattice relaxation, charge state, and doping conditions. These findings establish trigonal selenium as a defect-tolerant wide-band-gap absorber and provide transferable design principles for optimizing next-generation photovoltaic materials for tandem and indoor applications.

cond-mat.mtrl-sci↗

arXiv2023

Imperfections are not 0 K: free energy of point defects in crystals

Defects determine many important properties and applications of materials, ranging from doping in semiconductors, to conductivity in mixed ionic-electronic conductors used in batteries, to active sites in catalysts. The theoretical description of defect formation in crystals has evolved substantially over the past century. Advances in supercomputing hardware, and the integration of new computational techniques such as machine learning, provide an opportunity to model longer length and time-scales than previously possible. In this Tutorial Review, we cover the description of free energies for defect formation at finite temperatures, including configurational (structural, electronic, spin) and vibrational terms. We discuss challenges in accounting for metastable defect configurations, progress such as machine learning force fields and thermodynamic integration to directly access entropic contributions, and bottlenecks in going beyond the dilute limit of defect formation. Such developments are necessary to support a new era of accurate defect predictions in computational materials chemistry.

cond-mat.mtrl-sci↗

arXiv2022

Band gap opening from displacive instabilities in layered covalent-organic frameworks $^\dag$

Covalent organic frameworks (COFs) offer a high degree of chemical and structural flexibility. There is a large family of COFs built from 2D sheets that are stacked to form extended crystals. While it has been common to represent the stacking as eclipsed with one repeating layer ("AA"), there is growing evidence that a more diverse range of stacking sequences is accessible. Herein, we report a computational study of layer stacking in two prototypical COFs, Tp-Azo and DAAQ-TFP, which have shown high performance as Li-ion battery electrodes. We find a striking preference for slipped structures with horizontal offsets between layers ranging from 1.7 \r{A} to 3.5 \r{A} in a potential energy minimum that forms a low energy ring. The associated symmetry breaking results in a pronounced change in the underlying electronic structure. A band gap opening of 0.8 - 1.4 eV is found due to modifications of the underlying valence and conduction band dispersion as explained from changes in the $\pi$ orbital overlap. The implications for the screening and selection of COF for energy applications are discussed.

cond-mat.mtrl-sci↗

arXiv2021

Chemical bonding origin of the thermoelectric power factor in Half-Heusler semiconductors

Intermetallic semiconductors with the cubic Half-Heusler structure (XYZ) have excellent thermoelectric properties. This has been attributed to the high degeneracy of the carrier pockets in the band structure, but large differences are found between different material compositions. Half-Heuslers are often interpreted within Zintl chemistry, making a clear distinction between an electropositive cation ($X^{n+}$) and an extended polyanion ($YZ^{n-}$). Based on quantitative real space chemical bonding analysis, we unravel large degrees of covalent bonding between the formal cation and anion, making the Zintl distinction clearly invalid. This covalence is shown to strongly affect the band structure, thermoelectric properties and response properties in the materials, with improved thermoelectric properties observed for those materials that least follow the Zintl concept. This expands our knowledge of the chemical bonding motifs governing physical properties, and gives a critical view on the simplistic chemical concepts too often applied for design of complex materials.

cond-mat.mtrl-sci↗

arXiv2020

Expression and interactions of stereo-chemically active lone pairs and their relation to structural distortions and thermal conductivity

Stereo-chemically active lone pairs are typically described as an important non-bonding effect, and large interest has centered on understanding the derived effect of lone pair expression on physical properties such as the thermal conductivity. To manipulate such properties, it is essential to understand the conditions that lead to lone pair expression and to provide a quantitative chemical description. Here we first use density functional theory calculations to establish the presence of stereo-chemically active lone pairs on antimony in $\text{MnSb}_{2}\text{O}_{4}$. The lone pairs are formed through a similar mechanism to those in binary post-transition metal compounds in an oxidation state of two less than their main group number, where the degree of orbital interaction determines the expression of the lone pair. In $\text{MnSb}_{2}\text{O}_{4}$ the Sb lone pairs interact through a void space in the crystal structure, and they minimize their mutual repulsion by introducing a deflection angle. This angle increases significantly with decreasing Sb-Sb distance, thus showing the highly destabilizing nature of the lone pair interactions. Analysis of the chemical bonding in the structure shows that it is dominated by polar covalent interactions. A database search of related ternary chalcogenide structures shows that for structures with a lone pair the degree of lone pair expression is largely determined by whether the antimony-chalcogen units are connected or not, suggesting a cooperative effect. Isolated $\text{SbX}_3$ units have larger X-Sb-X bond angles, and therefore weaker lone pair expression than connected units. Since increased lone pair expression is equivalent to an increased orbital interaction (covalent bonding), which typically leads to increased heat conduction, this can explain the previously established correlation between larger bond angles and lower thermal conductivity.

cond-mat.mtrl-sci↗

arXiv2018

Relating chemical bonding to physical properties: The origin of unexpected isotropic properties in layered materials

Layered materials span a very broad range of solids ranging from van der Waals materials to highly complex crystal structures such as clays. They are commonly believed to have highly anisotropic properties, which is essentially attributed to weak interlayer interactions. The layered Mg3Sb2 structure is currently being intensely scrutinized due to its outstanding thermoelectric properties. Based on quantitative chemical bonding analysis we unravel that Mg3Sb2 exhibits a nearly isotropic three-dimensional (3D) bonding network with the interlayer and intralayer bonds being surprisingly similar, and these unique chemical bonding features are the origin of the nearly isotropic structural and thermal properties. The isotropic 3D bonding network is found to be broadly applicable to many Mg-containing compounds with the layered CaAl2Si2-type structure. Intriguingly, a parameter based on the electron density can be used as an indicator measuring the anisotropy of lattice thermal conductivity in layered structures. This work extends our understanding of structure and properties based on chemical bonding analysis, and it will guide the search for, and design of, layered materials with tailored anisotropic properties.

cond-mat.mtrl-sci↗